YOCKE AND COMPANY 

Final Report

UPDATES TO THE CARBON BOND 

CHEMICAL MECHANISM: CB05 

RT-04-00675 

Prepared for 

Deborah Luecken 

U.S. Environmental Protection Agency 

Research Triangle Park, NC 27703 

Prepared by 

Greg Yarwood and Sunja Rao 

ENVIRON International Corporation 

101 Rowland Way, Suite 220 

Novato, CA 94945 

Mark Yocke 

Yocke & Company 

101 Rowland Way 

Novato, CA 94945 

Gary Z. Whitten 

Smog Reyes 

112 Mesa 

Point Reyes Station, CA 94956 

December 8, 2005 

 101 Rowland Way, Suite 220, Novato, CA 94945 415.899.0703 
H:\EPA_CB4\Report\final\ACKNOWLEDGEMENT.doc 

ACKNOWLEDGEMENT 

The authors gratefully acknowledge contributions from several collaborators in this work. Dr. 

William Carter of U.C. Riverside (UCR) simulated smog chamber experiments performed at 

UCR. Mr. Ken Sexton of the University of North Carolina (UNC) provided assistance in 

simulating smog chamber experiments performed at UNC. Dr. Deborah Luecken and Dr. Golam 

Sarwar of U.S. EPA provided advice and review of the data, assumptions and interpretation of 

results for this study. 
H:\EPA_CB4\Report\final\ABSTRACT.doc 

ABSTRACT 

Updated versions of the Carbon Bond mechanism were developed for use in EPA atmospheric 

modeling studies. The new Carbon Bond mechanism is called CB05 because it was developed in 

2005. The CB05 is a condensed mechanism of atmospheric oxidant chemistry that provides a 

basis for computer modeling studies of ozone, particulate matter (PM), visibility, acid deposition 

and air toxics issues. Updates in CB05 compared to earlier CB4 mechanisms are: 

• Updated rate constants based on recent (2003 – 2005) IUPAC and NASA evaluations. 

• An extended inorganic reaction set for urban to remote tropospheric conditions. 

• NOx recycling reactions to represent the fate of NOx over multiple days. 

• Explicit organic chemistry for methane and ethane. 

• Explicit methylperoxy radical, methyl hydroperoxide and formic acid. 

• Lumped higher organic peroxides, organic acids and peracids. 

• Internal olefin (R-HC=CH-R) species called IOLE. 

• Higher aldehyde species ALDX making ALD2 explicitly acetaldehyde. 

• Higher peroxyacyl nitrate species from ALDX called PANX. 

• Lumped terpene species called TERP. 

• Optional mechanism extension for reactive chlorine chemistry. 

• Optional extended mechanism with explicit reactions for air-toxics. 

The core CB05 mechanism has 51 species and 156 reactions. The CB05 was evaluated against 

smog chamber data from the Universities of North Carolina and California at Riverside. An 

updated wall reaction mechanism was developed for the UNC chamber that improved 

performance in experiments that are sensitive to chamber radical sources. The addition of higher 

aldehyde (ALDX) and internal olefin (IOLE) species to CB05 improve mechanism performance 

for simulating these species groups. The addition of organic peroxide species improves the 

simulation of oxidants that are involved in PM sulfate formation. The addition of explicit 

methylperoxy radical improves the simulation of hydrogen peroxide under low NOx conditions. 

Two CB05 mechanism extensions were developed. The reactive chlorine chemistry mechanism 

can be used in conjunction with the CB05 core mechanism to model the impact of CL2 and/or 

HOCl emissions on oxidant formation and VOC decay rates. The explicit species extension can 

be used in conjunction with the CB05 (or another) core mechanism to model the following toxic 

species: primary formaldehyde, primary acetaldehyde, 1,3-butadiene, primary and secondary 

acrolein. Other explicit species are toluene, o-xylene, m-xylene, p-xylene, apha-pinene and betapinene. These include the main precursors to secondary organic aerosol (SOA) and could be 

used as the basis for refined modeling approach for SOA that is independent of the core 

mechanism selected (e.g., CB4, CB05 or SAPRC99). 
December 2005 

i 

TABLE OF CONTENTS 

Page 

1. INTRODUCTION................................................................................................................ 1-1 

History of CB4....................................................................................................................... 1-1 

2. MECHANISM UPDATES .................................................................................................. 2-1 

CB05 Core Mechanism.......................................................................................................... 2-1 

Extended Mechanism with Explicit Species........................................................................ 2-10 

Reactive Chlorine Chemistry............................................................................................... 2-13 

Chemical Species Mapping for CB05 Mechanisms ............................................................ 2-15 

3. CB05 IMPLEMENTATION TESTING............................................................................ 3-1 

Comparing CB05 to CB4....................................................................................................... 3-1

Rate Constant Comparisons................................................................................................... 3-5

Box Model Comparisons ....................................................................................................... 3-9

4. MECHANISM EVALUATION.......................................................................................... 4-1 

 UNC Chamber ....................................................................................................................... 4-1 

 UCR Chamber........................................................................................................................ 4-9 

5. SUMMARY AND RECOMMENDATIONS..................................................................... 5-1 

REFERENCES.......................................................................................................................... R-1 

APPENDICES 

Appendix A: Assignments from VOC Species to CB05 Model Species 

Appendix B: Chamber Simulations for the University of North Carolina (UNC) 

 Chamber with CB05 Organized by Chemical Compound Type 
December 2005 

ii 

TABLES 

Table 2-1. Species names for the CB05 core mechanism ..................................................... 2-1

Table 2-2. Reactions in the CB05 core mechanism .............................................................. 2-2

Table 2-3. Reactions in the extended CB05 mechanism that 

 may be added to the core mechanism. ............................................................... 2-10 

Table 2-4. Reactions in the CB05 reactive chlorine mechanism 

 that may be added to the CB05 core mechanism............................................... 2-13 

Table 2-5. Species added to CB05 by the reactive chlorine mechanism ............................ 2-14 

Table 3-1. VOC composition used for the box model comparison of CB4 and CB05......... 3-1 

Table 3-2. Comparison of CB05 thermal rate constants calculated 

 by SmogReyes and EPA for three different 

 temperature/pressure conditions (units are ppm and minutes) ............................ 3-6

Table 4-1. Wall reactions from the Jeffries, Voicu and Sexton (2002) 

 UNC chamber mechanisms that were changed for this project........................... 4-2 

Table 4-2. New wall reactions for the UNC chamber used in this project............................ 4-2 

Table 4-3. Compounds and numbers of UCR experiments included in 

 the comparison between CB05 and SAPRC99 mechanism performance ......... 4-12 

Table 4-4. Numbered UCR chamber experiments used to evaluate 

 the CB05 and SAPRC99 mechanisms, by compound ....................................... 4-13 

FIGURES 

Figure 3-1. Comparison of CB4 and CB05 ozone predictions for 

 urban MIR conditions. ......................................................................................... 3-2 

Figure 3-2. Comparison of CB4 and CB05 HNO3 predictions for 

 urban MIR conditions .......................................................................................... 3-3 

Figure 3-3. Comparison of CB4 and CB05 H2O2 predictions for 

 urban MIR conditions. ......................................................................................... 3-3 

Figure 3-4. Comparison of CB4 and CB05 ozone predictions for 

 urban MOIR conditions ....................................................................................... 3-4 

Figure 3-5. Comparison of CB4 and CB05 HNO3 predictions for 

 urban MOIR conditions ....................................................................................... 3-4 

Figure 3-6. Comparison of CB4 and CB05 H2O2 predictions for 

 urban MOIR conditions ....................................................................................... 3-5 

Figure 3-7. Comparison of results from the CMAQ and OZIPM box 

 models for NO, NO2 and O3 at 298 K and 1 atmosphere .................................. 3-10 

Figure 3-8. Comparison of results from the CMAQ and OZIPM box 

 models for HONO and HO2 at 298 K and 1 atmosphere................................... 3-10 

Figure 3-9. Comparison of results from the CMAQ and OZIPM box 

 models for NO, NO2 and O3 at 298 K and 0.5 atmosphere ............................... 3-11 

Figure 3-10. Comparison of results from the CMAQ and OZIPM box 

 models for NO, NO2 and O3 at 310K and 1 atmosphere ................................... 3-11 

Figure 4-1. Comparison of CB05 (top) and CB4-2002 (bottom) 

 simulations of UNC carbon monoxide experiment August 30, 1993 (red) ......... 4-3 

Figure 4-2. Comparison of CB05 (top) and CB4-2002 (bottom) 

 simulations of UNC carbon monoxide experiment August 30, 1996 (blue) ....... 4-4 
December 2005 

iii 

Figure 4-3. Comparison of CB05 (top) and CB4-2002 (bottom) 

 simulations of UNC experiment of September 4, 1997 (red chamber) 

 with trimethylacetaldehyde and Propionaldehyde............................................... 4-5 

Figure 4-4. Comparison of CB05 (top) and CB4-2002 (bottom) 

 simulations of UNC experiment October 16, 1996 (blue chamber) 

 with propene, 1-butene and 1-pentene................................................................. 4-6 

Figure 4-5. Comparison of CB05 (top) and CB4-2002 (bottom) 

 simulations of UNC experiment September 14, 1996 (blue chamber) 

 with an equimolar mixture of all butene isomers (1-butene, 

 cis-2-butene, trans-2-butene, isobutene).............................................................. 4-7 

Figure 4-6. SAPRC99 (left) and CB05 (right) simulation of a carbon 

 monoxide experiment in the EPA chamber at UCR .......................................... 4-14 

Figure 4-7. SAPRC99 simulation of four formaldehyde experiments 

 in the EPA chamber at UCR .............................................................................. 4-15 

Figure 4-8. CB05 simulation of four formaldehyde experiments 

 in the EPA chamber at UCR .............................................................................. 4-16 

Figure 4-9. SAPRC99 (left) and CB05 (right) simulation of an 

 ethene experiment in the EPA chamber at UCR................................................ 4-17 

Figure 4-10. SAPRC99 (left) and CB05 (right) simulation of a propene 

 experiment in the EPA chamber at UCR ........................................................... 4-17 

Figure 4-11. SAPRC99 (left) and CB05 (right) simulation of a butane 

 experiment in the EPA chamber at UCR ........................................................... 4-18 

Figure 4-12. SAPRC99 simulation of two toluene experiments 

 in the EPA chamber at UCR .............................................................................. 4-19 

Figure 4-13. CB05 simulation of two toluene experiments in the EPA chamber at UCR ..... 4-20 

Figure 4-14. SAPRC99 simulation of two xylene experiments 

 in the EPA chamber at UCR. ............................................................................. 4-21 

Figure 4-15. CB05 simulation of two xylene experiments in the EPA chamber at UCR. ..... 4-22 

Figure 4-16. Bias in oxidant production (O3-NO) at hours 1-6 in 

 UCR chamber experiments for the CB05 and SAPRC99 

 mechanisms, by compound................................................................................ 4-23 
December 2005 

H:\EPA_CB4\Report\final\Sec1_Intro.doc 1-1 

1. INTRODUCTION 

The goals of this study were to develop updated versions of the Carbon Bond mechanism for use 

in EPA atmospheric modeling studies. The starting point for this study was version 4 of the 

Carbon Bond mechanism (CB4) developed in the late 1980s (Gery et al., 1989) as updated in the 

mid 1990s for EPA’s “OTAG” study. An overview of the development history of CB4 and 

related mechanisms is given below. 

The new version of the Carbon Bond mechanism is called CB05 because it was developed in 

2005. The CB05 is a condensed mechanism of atmospheric oxidant chemistry that provides a 

basis for computer modeling studies of ozone, particulate matter (PM), visibility, acid deposition 

and air toxics issues. The CB05 mechanism updates developed for this study are as follows: 

1. Incorporating current kinetic and photolysis data in the core mechanism. 

2. Extending the chemical mechanism to better support PM modeling needs such as 

formation of secondary organic aerosols (SOA). 

3. Adding extra species and reactions to treat a number of volatile organic compounds 

(VOCs) explicitly for modeling air toxics. 

4. Accounting for the role of reactive chlorine emissions in VOC degradation and oxidant 

chemistry. 

The CB05 mechanism updates are discussed further in Section 2. 

HISTORY OF CB4 

EPA sponsored the development of version IV of the Carbon Bond (CB4) in the late 1980’s for 

use in urban and regional photochemical modeling and Gery et al., (1989), published the 

mechanism. The regional models of the late 1980’s that utilized CB4 were more limited in 

domain extent than current regional models (e.g., formulated for the planetary boundary layer 

and not the upper troposphere) and the original CB4 was more appropriate for urban than 

regional scale modeling. 

EPA made limited updates to the CB4 mechanism in the early 1990s. The three main updates 

were to PAN chemistry, radical termination reactions and isoprene chemistry and they 

culminated in the version of CB4 used for the Ozone Transport Assessment Group (OTAG) 

modeling and EPA’s NOx SIP call. Two other versions of CB4 that have appeared since the 

OTAG version are CBM-Z and CB2002. These mechanisms are reviewed briefly below. 

The Urban Airshed Model Version of CB4 

The EPA’s Urban Airshed Model (UAM-IV; Morris and Myers, 1990) had the first widely used 

version of the CB4 mechanism. Changes from the Gery et al. (1989) mechanism were the 

inclusion of explicit chemistry for methanol and ethanol and an update to the PAN chemistry. 

Dodge (1991) updated the PAN chemistry for CB4 because the Gery et al. (1989) mechanism 

had incorrect temperature dependencies for PAN formation (Tuazon, Carter and Atkinson, 

1991). 
December 2005 

H:\EPA_CB4\Report\final\Sec1_Intro.doc 1-2 

The OTAG Version of CB4 

The OTAG version of CB4 had two updates were made to better represent regional scale oxidant 

formation in the eastern US where high isoprene levels occur and rural areas have relatively low 

NOx concentrations. Yarwood updated the radical-radical termination reactions (among HO2

and RO2 radicals) to better represent oxidant formation under conditions of low NOx (Yarwood 

and Burton, 1994). Whitten updated the isoprene chemistry in the CB4 (Whitten et al., 1996) to 

reflect newer scientific data on the products and mechanisms of isoprene oxidation (Carter and 

Atkinson, 1996). The updated isoprene mechanism is a translation from SAPRC to CB4 species 

of Carter’s condensed “1-product” isoprene mechanism (Carter, 1996). 

CBM-Z – Pacific Northwest National Laboratory 

The Pacific Northwest National Laboratory (PNNL) has developed a mechanism based on the 

Carbon Bond approach called CBM-Z (Zaveri and Peters, 1999). Changes in CBM-Z were 

intended to update the mechanism from the published Gery et al., (1989) version and improve 

performance for regional scale modeling, and included: 

• Revised inorganic chemistry. 

• Explicit treatment of the lesser reactive alkanes - methane and ethane. 

• Revised parameterizations of the reactive paraffin, olefin, and aromatic reactions. 

• Inclusion of alkyl and acyl peroxy radical interactions and their reactions with the NO3

radical. 

• Inclusion of organic hydroperoxides. 

• Isoprene chemistry based on the condensed one-product mechanism of Carter (1996). 

The CBM-Z and CB4 were evaluated against smog chamber data from the TVA chamber and 

showed improved performance for CBM-Z on these chamber experiments. Sensitivity tests 

showed larger differences between CBM-Z and CB4 for regional modeling conditions than for 

urban or smog chamber conditions. One factor that contributed to differences under regional 

conditions (Zaveri and Peters, 1999) was the inclusion in CBM-Z of reactions for organic 

nitrates that slowly recycle nitrogen from an inactive form (organic nitrates) to an active form 

(NOx). 

CB2002 – University of North Carolina 

In late 1990s, UNC started to update and re-evaluate the CB4 mechanism against smog chamber 

data. UNC’s approach was to retain the overall structure of CB4 but update rate constants and 

some product yields based on recent data. The first mechanism produced by UNC was called 

CB99. Unfortunately, the CB99 work was completed just as literature values for a critical rate 

constant (OH + NO2) changed. UNC repeated the work with the new OH + NO2 rate constant 

and developed CB2002 to supercede CB99 (Jeffries, Voicu, and Sexton, 2002). The CB2002 

was evaluated against UNC smog chamber data as described in detail in Jeffries, Voicu, and 

Sexton (2002). 
December 2005 

H:\EPA_CB4\Report\final\Sec1_Intro.doc 1-3 

The main changes between CB2002 and CB4 were: 

• Updated inorganic reaction rate constants with new reactions for NO3 reacting with OH, 

HO2 and itself, and O3 reacting with O(3P). 

• A new HONO photolysis reaction yielding NO2 and H-atoms. IUPAC (2004) now 

recommends setting this reaction to zero for tropospheric conditions. 

• New rate constants for N2O5 reacting with water (Wahner et al., 1998). This update also 

includes a reaction of N2O5 with water dimers (i.e., N2O5 + H2O + H2O). 

• Lower rate constants for radical-radical termination reactions involving XO2 and HO2. 

• New rate constants for all olefin reactions involving ETH, OLE and ISOP. 

• New products for reactions of ETH and OLE. 
December 2005 

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 2-1 

2. MECHANISM UPDATES 

The main CB05 mechanism is referred to as the core mechanism. There are two extensions to 

the core mechanism for modeling explicit species (e.g., toxics) and reactive chlorine chemistry. 

The core mechanism and extensions are described below. Finally, the process for mapping “real 

species” to CB05 “model species” is discussed (e.g., for emission inventory modeling). 

CB05 CORE MECHANISM 

The core CB05 mechanism has 51 chemical species (Table 2-1) and 156 reactions (Table 2-2). 

The changes in the mechanism from CB4 (Gery et al., 1989) fall into the following categories 

that are discussed following Tables 2-1 and 2-2. 

 

• Kinetic Updates 

• Photolysis Updates 

• Extended Inorganic Reaction Set 

• Simple Alkanes (Methane and Ethane) 

• Higher Aldehydes 

• Alkenes with Internal Double Bonds 

• Oxygenated Products and Intermediates 

• Terpene Chemistry 

Table 2-1. Species names for the CB05 core mechanism. 

Species 

Name Description 

Number of 

Carbons 

NO Nitric oxide 0 

NO2 Nitrogen dioxide 0 

O3 Ozone 0 

O Oxygen atom in the O3(P) electronic state 0 

O1D Oxygen atom in the O1(D) electronic state 0 

OH Hydroxyl radical 0 

HO2 Hydroperoxy radical 0 

H2O2 Hydrogen peroxide 0 

NO3 Nitrate radical 0 

N2O5 Dinitrogen pentoxide 0 

HONO Nitrous acid 0 

HNO3 Nitric acid 0 

PNA Peroxynitric acid (HNO4) 0 

CO Carbon monoxide 1 

FORM Formaldehyde 1 

ALD2 Acetaldehyde 2 

C2O3 Acetylperoxy radical 2 

PAN Peroxyacetyl nitrate 2 

ALDX Propionaldehyde and higher aldehydes 2 

CXO3 C3 and higher acylperoxy radicals 2 

PANX C3 and higher peroxyacyl nitrates 2 

XO2 NO to NO2 conversion from alkylperoxy (RO2) radical 0 

XO2N NO to organic nitrate conversion from alkylperoxy (RO2) radical 0 

NTR Organic nitrate (RNO3) 1 

ETOH Ethanol 2 
December 2005 

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 2-2 

Species 

Name Description 

Number of 

Carbons 

CH4 Methane 1 

MEO2 Methylperoxy radical 1 

MEOH Methanol 1 

MEPX Methylhydroperoxide 1 

FACD Formic acid 1 

ETHA Ethane 2 

ROOH Higher organic peroxide 1 

AACD Acetic and higher carboxylic acids 2 

PACD Peroxyacetic and higher peroxycarboxylic acids 2 

PAR Paraffin carbon bond (C-C) 1 

ROR Secondary alkoxy radical 0 

ETH Ethene 2 

OLE Terminal olefin carbon bond (R-C=C) 2 

IOLE Internal olefin carbon bond (R-C=C-R) 4 

ISOP Isoprene 5 

ISPD Isoprene product (lumped methacrolein, methyl vinyl ketone, etc.) 4 

TERP Terpene 10 

TOL Toluene and other monoalkyl aromatics 7 

XYL Xylene and other polyalkyl aromatics 8 

CRES Cresol and higher molecular weight phenols 8 

TO2 Toluene-hydroxyl radical adduct 7 

OPEN Aromatic ring opening product 4 

CRO Methylphenoxy radical 7 

MGLY Methylglyoxal and other aromatic products 3 

SO2 Sulfur dioxide 0 

SULF Sulfuric acid (gaseous) 0 

Table 2-2. Reactions in the CB05 core mechanism. 

Label Reactants Products Rate Expression Notes 

R1 NO2 NO + O 1.0 x <NO2_SAPRC99> 20 

R2 O+O2+M O3 + M 6.0E–34^–2.4 1 

R3 O3+NO NO2 3.0E–12 @ 1500 1 

R4 O+NO2 NO 5.6E–12 @ –180 1 

R5 O+NO2 NO3 2.5E–31^–1.8 & 

2.2E–11^–0.7 

1 

R6 O+NO NO2 9.0E–32^–1.5 & 3.0E–11 1 

R7 NO2+O3 NO3 1.2E–13 @ 2450 1 

R8 O3 O 1.0 x <O3_O3P_IUPAC05> 2 

R9 O3 O1D 1.0 x <O3_O1D_IUPAC05> 2 

R10 O1D+M O + M 2.1E–11 @ –102 1 

R11 O1D+H2O 2*OH 2.20E–10 1 

R12 O3+OH HO2 1.7E–12 @ 940 1 

R13 O3+HO2 OH 1.0E–14 @ 490 1 

R14 NO3 NO2 + O 1.0 x <NO3NO2_SAPRC99> 20 

R15 NO3 NO 1.0 x <NO3NO_SAPRC99> 20 

R16 NO3+NO 2*NO2 1.5E–11 @ –170 1 

R17 NO3+NO2 NO + NO2 4.5E–14 @ 1260 1 

R18 NO3+NO2 N2O5 2.0E–30^–4.4 & 1 
December 2005 

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 2-3 

Label Reactants Products Rate Expression Notes 

1.4E–12^–0.7 

R19 N2O5+H2O 2*HNO3 2.50E–22 2 

R20 N2O5+H2O+H2O 2*HNO3 1.80E–39 2 

R21 N2O5 NO3 + NO2 1E–03^–3.5 @ 11000 & 

9.7E14^0.1 @ 11080 & 

0.45 & 1.0 

2 

R22 NO+NO+O2 2*NO2 3.3E–39 @ –530 2 

R23 NO+NO2+H2O 2*HONO 5.00E–40 3 

R24 NO+OH HONO 7.0E–31^–2.6 & 

3.6E–11^–0.1 

1 

R25 HONO NO + OH 1.0 x <HONO_IUPAC05> 2 

R26 OH+HONO NO2 1.8E–11 @ 390 1 

R27 HONO+HONO NO + NO2 1.00E–20 4 

R28 NO2+OH HNO3 2.0E–30^–3.0 & 2.5E–11 1 

R29 OH+HNO3 NO3 %2 2.4E–14 @ –460 & 

2.7E–17 @ –2199 & 

6.5E–34 @ –1335 

1 

R30 HO2+NO OH + NO2 3.5E–12 @ –250 1 

R31 HO2+NO2 PNA 1.8E–31^–3.2 & 4.7E–12 & 

0.6 

2 

R32 PNA HO2 + NO2 4.1E–5 @ 10650 & 

4.8E15 @ 11170 & 0.6 

2 

R33 OH+PNA NO2 1.3E–12 @ –380 1 

R34 HO2+HO2 H2O2 %3 2.3E–13 @ –600 & 

1.7E–33 @ –1000 

1 

R35 HO2+HO2+H2O H2O2 %3 3.22E–34 @ –2800 & 

2.38E–54 @ –3200 

1 

R36 H2O2 2*OH 1.0 x <H2O2_SAPRC99> 20 

R37 OH+H2O2 HO2 2.9E–12 @ 160 1 

R38 O1D+H2 OH + HO2 1.10E–10 1 

R39 OH+H2 HO2 5.5E–12 @ 2000 1 

R40 OH+O HO2 2.2E–11 @ –120 1 

R41 OH+OH O 4.2E–12 @ 240 1 

R42 OH+OH H2O2 6.9E–31^–1.0 & 2.6E–11^0 1 

R43 OH+HO2 4.8E–11 @ –250 1 

R44 HO2+O OH 3.0E–11 @ –200 1 

R45 H2O2+O OH + HO2 1.4E–12 @ 2000 1 

R46 NO3+O NO2 1.00E–11 1 

R47 NO3+OH HO2 + NO2 2.20E–11 1 

R48 NO3+HO2 HNO3 3.50E–12 1 

R49 NO3+O3 NO2 1.00E–17 5 

R50 NO3+NO3 2*NO2 8.5E–13 @ 2450 1 

R51 PNA 0.610*HO2 + 0.610*NO2 + 0.390*OH + 

0.390*NO3 

1.0 x <HO2NO2_IUPAC05> 2 

R52 HNO3 OH + NO2 1.0 x <HNO3_IUPAC05> 2 

R53 N2O5 NO2 + NO3 1.0 x <N2O5_IUPAC05> 2 

R54 XO2+NO NO2 2.6E–12 @ –365 6 
December 2005 

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 2-4 

Label Reactants Products Rate Expression Notes 

R55 XO2N+NO NTR 2.6E–12 @ –365 6 

R56 XO2+HO2 ROOH 7.5E–13 @ –700 7 

R57 XO2N+HO2 ROOH 7.5E–13 @ –700 7 

R58 XO2+XO2 6.80E–14 8 

R59 XO2N+XO2N 6.80E–14 8 

R60 XO2+XO2N 6.80E–14 8 

R61 NTR+OH HNO3 + HO2 + 0.330*FORM + 0.330*ALD2 + 

0.330*ALDX – 0.660*PAR 

5.9E–13 @ 360 9 

R62 NTR NO2 + HO2 + 0.330*FORM + 0.330*ALD2 + 

0.330*ALDX – 0.660*PAR 

1.0 x <NTR_IUPAC05> 28 

R63 ROOH+OH XO2 + 0.500*ALD2 + 0.500*ALDX 3.01E–12 @ –190 1 

R64 ROOH OH + HO2 + 0.500*ALD2 + 0.500*ALDX 1.0 x <COOH_SAPRC99> 20 

R65 OH+CO HO2 %3 1.44E–13 @ 0.0 & 

3.43E–33 @ 0.0 

2 

R66 OH+CH4 MEO2 2.45E–12 @ 1775 1 

R67 MEO2+NO FORM + HO2 + NO2 2.8E–12 @ –300 1 

R68 MEO2+HO2 MEPX 4.1E–13 @ –750 1 

R69 MEO2+MEO2 1.370*FORM + 0.740*HO2 + 0.630*MEOH 9.5E–14 @ –390 1 

R70 MEPX+OH 0.700*MEO2 + 0.300*XO2 + 0.300*HO2 3.8E–12 @ –200 1 

R71 MEPX FORM + HO2 + OH 1.0 x <COOH_SAPRC99> 20 

R72 MEOH+OH FORM + HO2 7.3E–12 @ 620 1 

R73 FORM+OH HO2 + CO 9.00E–12 1 

R74 FORM 2*HO2 + CO 1.0 x <HCHO_R_SAPRC99> 20 

R75 FORM CO 1.0 x <HCHO_M_SAPRC99> 20 

R76 FORM+O OH + HO2 + CO 3.4E–11 @ 1600 1 

R77 FORM+NO3 HNO3 + HO2 + CO 5.80E–16 1 

R78 FORM+HO2 HCO3 9.7E–15 @ –625 2 

R79 HCO3 FORM + HO2 2.4E+12 @ 7000 1 

R80 HCO3+NO FACD + NO2 + HO2 5.60E–12 1 

R81 HCO3+HO2 MEPX 5.6E–15 @ –2300 1 

R82 FACD+OH HO2 4.00E–13 1 

R83 ALD2+O C2O3 + OH 1.8E–11 @ 1100 1 

R84 ALD2+OH C2O3 5.6E–12 @ –270 1 

R85 ALD2+NO3 C2O3 + HNO3 1.4E–12 @ 1900 1 

R86 ALD2 MEO2 + CO + HO2 1.0 x <CCHO_R_SAPRC99> 20 

R87 C2O3+NO MEO2 + NO2 8.1E–12 @ –270 1 

R88 C2O3+NO2 PAN 2.7E–28^–7.1 & 

1.2E–11^–0.9 & 0.3 

2 

R89 PAN C2O3 + NO2 4.9E–3 @ 12100 & 

5.4E16 @ 13830 & 0.3 

2 

R90 PAN C2O3 + NO2 1.0 x <PAN_IUPAC05> 2 

R91 C2O3+HO2 0.800*PACD + 0.200*AACD + 0.200*O3 4.3E–13 @ –1040 1 

R92 C2O3+MEO2 0.900*MEO2 + 0.900*HO2 + FORM + 

0.100*AACD 

2.0E–12 @ –500 1 

R93 C2O3+XO2 0.900*MEO2 + 0.100*AACD 4.4E–13 @ –1070 2 
December 2005 

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 2-5 

Label Reactants Products Rate Expression Notes 

R94 C2O3+C2O3 2*MEO2 2.9E–12 @ –500 1 

R95 PACD+OH C2O3 4.0E–13 @ –200 10 

R96 PACD MEO2 + OH 0.0 x <COOH_SAPRC99> 20 

R97 AACD+OH MEO2 4.0E–13 @ –200 1 

R98 ALDX+O CXO3 + OH 1.3E–11 @ 870 11 

R99 ALDX+OH CXO3 5.1E–12 @ –405 2 

R100 ALDX+NO3 CXO3 + HNO3 6.50E–15 2 

R101 ALDX MEO2 + CO + HO2 1.0 x <C2CHO_SAPRC99> 20 

R102 CXO3+NO ALD2 + NO2 + HO2 + XO2 6.7E–12 @ –340 2 

R103 CXO3+NO2 PANX 2.7E–28^–7.1 & 

1.2E–11^–0.9 & 0.3 

12 

R104 PANX CXO3 + NO2 4.9E–3 @ 12100 & 

5.4E16 @ 13830 & 0.3 

12 

R105 PANX CXO3 + NO2 1.0 x <PAN_IUPAC05> 2 

R106 PANX+OH ALD2 + NO2 3.00E–13 13 

R107 CXO3+HO2 0.800*PACD + 0.200*AACD + 0.200*O3 4.3E–13 @ –1040 14 

R108 CXO3+MEO2 0.900*ALD2 + 0.900*XO2 + HO2 + 0.100*AACD 

+ 0.100*FORM 

2.0E–12 @ –500 15 

R109 CXO3+XO2 0.900*ALD2 + 0.100*AACD 4.4E–13 @ –1070 16 

R110 CXO3+CXO3 2*ALD2 + 2*XO2 + 2*HO2 2.9E–12 @ –500 1 

R111 CXO3+C2O3 MEO2 + XO2 + HO2 + ALD2 2.9E–12 @ –500 1 

R112 PAR+OH 0.870*XO2 + 0.130*XO2N + 0.110*HO2 + 

0.060*ALD2 – 0.110*PAR + 0.760*ROR + 

0.050*ALDX 

8.10E–13 17 

R113 ROR 0.960*XO2 + 0.600*ALD2 + 0.940*HO2 –

2.100*PAR + 0.040*XO2N + 0.020*ROR + 

0.500*ALDX 

1.0E+15 @ 8000 17 

R114 ROR HO2 1.60E+03 17 

R115 ROR+NO2 NTR 1.50E–11 17 

R116 O+OLE 0.200*ALD2 + 0.300*ALDX + 0.300*HO2 + 

0.200*XO2 + 0.200*CO + 0.200*FORM + 

0.010*XO2N + 0.200*PAR + 0.100*OH 

1.E–11 @ 280 18 

R117 OH+OLE 0.800*FORM + 0.330*ALD2 + 0.620*ALDX + 

0.800*XO2 + 0.950*HO2 – 0.700*PAR 

3.20E–11 21 

R118 O3+OLE 0.180*ALD2 + 0.740*FORM + 0.320*ALDX + 

0.220*XO2 + 0.100*OH + 0.330*CO + 

0.440*HO2 – PAR 

6.5E–15 @ 1900 22 

R119 NO3+OLE NO2 + FORM + 0.910*XO2 + 0.090*XO2N + 

0.560*ALDX + 0.350*ALD2 – PAR 

7E–13 @ 2160 23 

R120 O+ETH FORM + 1.700*HO2 + CO + 0.700*XO2 + 

0.300*OH 

1.04E–11 @ 792 4 

R121 OH+ETH XO2 + 1.560*FORM + 0.220*ALDX + HO2 1.0E–28^–0.8 & 8.8E–12 1 

R122 O3+ETH FORM + 0.630*CO + 0.130*HO2 + 0.130*OH + 

0.370*FACD 

1.2E–14 @ 2630 1 

R123 NO3+ETH NO2 + XO2 + 2.0*FORM 3.3E–12 @ 2880 2 

R124 IOLE+O 1.240*ALD2 + 0.660*ALDX + 0.100*HO2 + 

0.100*XO2 + 0.100*CO + 0.100*PAR 

2.3E–11 26 

R125 IOLE+OH 1.300*ALD2 + 0.700*ALDX + HO2 + XO2 1.0E–11 @ –550 26 

R126 IOLE+O3 0.650*ALD2 + 0.350*ALDX + 0.250*FORM + 

0.250*CO + 0.500*O + 0.500*OH + 0.500*HO2 

8.4E–15 @ 1100 26 
December 2005 

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 2-6 

Label Reactants Products Rate Expression Notes 

R127 IOLE+NO3 1.180*ALD2 + 0.640*ALDX + HO2 + NO2 9.6E–13 @ 270 26 

R128 TOL+OH 0.440*HO2 + 0.080*XO2 + 0.360*CRES + 

0.560*TO2 

1.8E–12 @ –355 24 

R129 TO2+NO 0.900*NO2 + 0.900*HO2 + 0.900*OPEN + 

0.100*NTR 

8.10E–12 17 

R130 TO2 CRES + HO2 4.2 17 

R131 OH+CRES 0.400*CRO + 0.600*XO2 + 0.600*HO2 + 

0.300*OPEN 

4.10E–11 17 

R132 CRES+NO3 CRO + HNO3 2.20E–11 17 

R133 CRO+NO2 NTR 1.40E–11 17 

R134 CRO+HO2 CRES 5.50E–12 25 

R135 OPEN C2O3 + HO2 + CO 9.0 x <HCHO_R_SAPRC99> 20 

R137 OPEN+O3 0.030*ALDX + 0.620*C2O3 + 0.700*FORM + 

0.030*XO2 + 0.690*CO + 0.080*OH + 

0.760*HO2 + 0.200*MGLY 

5.4E–17 @ 500 17 

R138 OH+XYL 0.700*HO2 + 0.500*XO2 + 0.200*CRES + 

0.800*MGLY + 1.100*PAR + 0.300*TO2 

1.7E–11 @ –116 17 

R139 OH+MGLY XO2 + C2O3 1.7E–11 17 

R140 MGLY C2O3 + HO2 + CO 1.0 x <MGLY_IUPAC05> 2 

R141 O+ISOP 0.750*ISPD + 0.500*FORM + 0.250*XO2 + 

0.250*HO2 + 0.250*CXO3 + 0.250*PAR 

3.60E–11 19 

R142 OH+ISOP 0.912*ISPD + 0.629*FORM + 0.991*XO2 + 

0.912*HO2 + 0.088*XO2N 

2.54E–11 @ –407.6 19 

R143 O3+ISOP 0.650*ISPD + 0.600*FORM + 0.200*XO2 + 

0.066*HO2 + 0.266*OH + 0.200*CXO3 + 

0.150*ALDX + 0.350*PAR + 0.066*CO 

7.86E–15 @ 1912 19 

R144 NO3+ISOP 0.200*ISPD + 0.800*NTR + XO2 + 0.800*HO2 + 

0.200*NO2 + 0.800*ALDX + 2.400*PAR 

3.03E–12 @ 448 19 

R145 OH+ISPD 1.565*PAR + 0.167*FORM + 0.713*XO2 + 

0.503*HO2 + 0.334*CO + 0.168*MGLY + 

0.252*ALD2 + 0.210*C2O3 + 0.250*CXO3 + 

0.120*ALDX 

3.36E–11 19 

R146 O3+ISPD 0.114*C2O3 + 0.150*FORM + 0.850*MGLY + 

0.154*HO2 + 0.268*OH + 0.064*XO2 + 

0.020*ALD2 + 0.360*PAR + 0.225*CO 

7.10E–18 19 

R147 NO3+ISPD 0.357*ALDX + 0.282*FORM + 1.282*PAR + 

0.925*HO2 + 0.643*CO + 0.850*NTR + 

0.075*CXO3 + 0.075*XO2 + 0.150*HNO3 

1.00E–15 19 

R148 ISPD 0.333*CO + 0.067*ALD2 + 0.900*FORM + 

0.832*PAR + 1.033*HO2 + 0.700*XO2 + 

0.967*C2O3 

0.0036 x 

<ACROLEIN_SAPRC99> 

20 

R149 TERP+O 0.150*ALDX + 5.12*PAR 3.60E–11 20 

R150 TERP+OH 0.750*HO2 + 1.250*XO2 + 0.250*XO2N + 

0.280*FORM + 1.66*PAR + 0.470*ALDX 

1.5E–11 @ –449 20 

R151 TERP+O3 0.570*OH + 0.070*HO2 + 0.760*XO2 + 

0.180*XO2N + 0.240*FORM + 0.001*CO + 

7.000*PAR + 0.210*ALDX + 0.390*CXO3 

1.2E–15 @ 821 20 

R152 TERP+NO3 0.470*NO2 + 0.280*HO2 + 1.030*XO2 + 

0.250*XO2N + 0.470*ALDX + 0.530*NTR 

3.7E–12 @ –175 20 

R153 SO2+OH SULF + HO2 3.0E–31^–3.3 & 1.5E–12 1 

R154 OH+ETOH HO2 + 0.900*ALD2 + 0.050*ALDX + 

0.100*FORM + 0.100*XO2 

6.9E–12 @ 230 1 

R155 OH+ETHA 0.991*ALD2 + 0.991*XO2 + 0.009*XO2N + HO2 8.7E–12 @ 1070 1 
December 2005 

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 2-7 

Label Reactants Products Rate Expression Notes 

R156 NO2+ISOP 0.200*ISPD + 0.800*NTR + XO2 + 0.800*HO2 + 

0.200*NO + 0.800*ALDX + 2.400*PAR 

1.50E–19 19 

Table Notes: 

Rate constants are in units of molecules cm-3 and seconds-1

Read rate expressions as follows: 

 A / <J_label> k = A x j 

 A @ E k = A x exp(–E/T) 

 A ^ B @ E k = A x (T/300)B

 x exp(–E/T) 

 Ao ^ Bo @ Eo

 & 

A∞ ^ B∞ @ E∞

 & 

F & n 

[ ]

[ ] k

k M

kM k

F

o

o

G = + ∞

⎡

⎣

⎢ ⎤

⎦

⎥ 1 / where 

( [ ] ) G

kM k

n

o

= +

∞ ⎛

⎝

⎜ ⎞

⎠

⎟ ⎡

⎣

⎢ ⎤

⎦

⎥

− −

1

2 1 log /

 %2 Ao @ Eo

 & 

A2 @ E2 & 

A3 @ E3

[ ]

[ ] k k

k M

kM k

o = + +

3

1 / 3 2

 %3 A1 @ E1 & 

A2 @ E2

k = k1 + k2 [M] 

1 Rate constant from NASA/JPL (2003) 

2 Rate constant from IUPAC (2005) 

3 Kaiser and Wu (1977) 

4 Jeffries et al. (2002) 

5 Hjorth (1992) 

6 Based on NASA/JPL (2003) C2H5O2 + NO 

7 Based on NASA/JPL (2003) C2H5O2 + HO2 

8 Based on NASA/JPL (2003) C2H5O2 + C2H5O2 

9 Average based on NASA/JPL (2003) CH3/C2H5 nitrates 

10 Same as AACD+OH 

11 Herron (1988) 

12 Same as for PAN 

13 Average based on NASA/JPL (2003) CH3/C2H5 nitrate ratio and IUPAC (2005) PAN+OH 

14 NASA/JPL (2003) for CH3C(O)OO + HO2 

15 NASA/JPL (2003) for CH3C(O)OO + CH3O2 

16 IUPAC (2005) for CH3C(O)OO 

17 Gery et al. (1989) 

18 Cvetanovic (1987) 

19 Atkinson and Carter (1994) single lumped product mechanism for isoprene. 

20 SAPRC99 

21 Consistent with IUPAC (2005) high-pressure limit for OH + propene. Falloff from the highpressure limit isn’t significant in the troposphere. Stoichiometric coefficients consistent with 

Atkinson (1997) and those developed and tested by Adelmann (1999). 

22 Rate constant consistent with IUPAC (2005) for O3 + propene. Products based on Gery et al. 

(1989) assuming a 2 to 1 product ratio of higher aldehydes (ALDX) to acetaldehyde (ALD2). 

23 Rate constant from Canosa-Mas et al. (1991) for minor pathway. May need future adjustment. 

24 Rate constant from Le Bras (1997), products from Gery et al. (1989). 

25 Adelmann (1999). 

26 Ligocki, et al. (2002). 

27 Homogeneous gas-phase reactions of N2O5 with water measured by Wahner, Mentel and Sohn 

(1998) and selected by IUPAC (2005). Rate contributions from heterogeneous reactions (see 

IUPAC 2005) may be added to the homogeneous rate. 

28 IUPAC (2005) photolysis data for isopropyl nitrate. 
December 2005 

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 2-8 

Kinetic Data 

Kinetic data for rate constant expressions were updated from the most recent evaluations by the 

IUPAC and NASA/JPL review panels, as detailed in the notes to Table 2-2. In general, values 

from IUPAC (2005) were selected. NASA/JPL (2003) values were used in some cases where 

IUPAC did not provide evaluated data. 

Photolysis Data 

Mechanism specific data required to calculate photolysis rates are absorption cross-sections and 

quantum yields. Photolysis data for CB05 are from the IUPAC (2005) evaluation or the 

SAPRC99 chemical mechanism (Carter, 2000). In general, data were used from SAPRC99 

unless the IUPAC (2005) recommendations were found to be significantly different. Using the 

same data as SAPRC99 simplifies implementation in air quality models and promotes 

consistency between two mechanisms that may be compared. 

Extended Inorganic Reaction Set 

Yarwood, Whitten and Rao (2005) reviewed the inorganic reaction set in the CB4 to identify 

reactions that should be added to account for conditions of temperature, pressure and chemical 

environment encountered in annual simulations at scales ranging from urban to continental. 

Seventeen reactions were added as discussed below. The extended inorganic reactions are 

summarized briefly here and discussed in more detail below. 

Reactions of molecular hydrogen (38 and 39) are somewhat important to odd-hydrogen (OH and 

HO2) for very dry conditions in the upper troposphere. Including hydrogen will allow the air 

quality impacts of hydrogen as an alternative fuel to be evaluated. Hydrogen has a tropospheric 

background concentration of about 0.6 ppm (Novelli et al, 1999). 

Reactions 40 to 45 involving odd-oxygen and odd-hydrogen species may be important for 

pristine conditions such as the upper troposphere. Including these reactions provides a more 

complete description of hydroxyl radical (OH) chemistry in the upper troposphere to improve 

modeling for persistent air toxics and mercury. 

Additional NO3 radical reactions (46 to 50) improve nighttime chemistry. NO3 radical is the 

main driver for atmospheric chemistry at night and including additional NO3 removal reactions 

improves the calculation of nighttime destruction rates for several types of reactive hydrocarbons 

(e.g., aldehydes, olefins) and for NOx (via NO3 and N2O5 reactions). 

Additional NOx recycling reactions (51 to 53 and 61 to 62) improve the representation of the fate 

of NOx over multi-day timescales by slowly recycling nitrogen from inactive forms of NOz to 

NOx. Reactions 51 and 53 are potentially important for very cold conditions such as the upper 

troposphere. Reactions 52, 61 and 62 of nitric acid and organic nitrates are potentially important 

to regional ozone and oxidant chemistry in the lower troposphere (Zaveri and Peters, 1999). 
December 2005 

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 2-9 

Simple Alkanes (Methane and Ethane) 

Explicit reactions were added for OH with methane (CH4) and ethane (ETHA) to better describe 

the chemistry in remote atmospheres. 

Higher Aldehydes 

A new higher aldehyde species (ALDX) was added based on propionaldehyde chemistry 

(Ligocki and Whitten, 1992). Note that ALDX and related species contain two carbon atoms, 

not three, because this simplifies. Species related to ALDX are the corresponding peroxyacyl 

radicals (CXO3), peroxynitrates (PANX), carboxylic acids (AACD) and peroxycarboxylic acids 

(PACD). The species ALD2 and related species (C2O3 and PAN) now explicitly represent the 

chemistry of acetaldehyde. In important difference between higher aldehydes and acetaldehyde 

is that they photolyse more rapidly because higher aldehydes have larger quantum yields than 

acetaldehyde. The benefits of including the lumped higher aldehyde (ALDX) in CB05 are that 

acetaldehyde becomes explicit for air toxics modeling, faster photolysis rates for higher 

aldehydes are better represented, and the degradation sequence for higher aldehydes becomes 

deeper (ALDX to ALD2 to FORM). ALDX also improves the representation of internal olefins, 

as discussed next. 

Alkenes with Internal Double Bonds 

A new species (IOLE) was added to represent alkenes with internal double bonds (internal 

olefins) such as 2-butenes. IOLE is four carbon species. Internal olefins react very rapidly to 

produce photolytic products (aldehydes). Internal olefins were represented by their aldehyde 

products (e.g., 2-butene was represented as 2 ALD2) in the CB4. Including the explicit species 

IOLE in CB05 better describes the rate (kinetics) of internal olefin reactions than the CB4 

approach. The IOLE chemistry is improved by having both acetaldehyde (ALD2) and lumped 

higher aldehydes (ALDX) as reaction products (Ligocki and Whitten, 1992). 

Oxygenated Products and Intermediates 

Several oxygenated species were added in conjunction with methane. Methylperoxy radicals 

were added as an explicit species (MEO2) rather than representing them by XO2. This change 

allows explicit representation of the products of the methylperoxy self-reaction (formaldehyde 

and methanol) and the reaction between methylperoxy and hydroperoxy radicals (methyl 

hydroperoxide). This change is expected to improve the representation of peroxide products that 

are important in sulfate production. 

Other organic peroxides also were added as products of peroxy radical reactions. Higher organic 

peroxides (ROOH) were added as products of XO2 reacting with HO2 with chemistry based on 

ethyl hydroperoxide reactions. Peroxycarboxylic acids were added based on peroxyacetic acid 

(PACD) as products of the reactions of peroxyacetyl (C2O3) and higher peroxyacyl (CXO3) 

radicals with HO2. 
December 2005 

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 2-10 

Two carboxylic acids were added as products of peroxy radical reactions. Formic acid (FACD) 

is produced by reactions of HO2 with formaldehyde. Higher carboxylic acids were added based 

on acetic acid (AACD) as products of the reactions of peroxyacetyl (C2O3) and higher 

peroxyacyl (CXO3) radicals with HO2. 

Terpene Chemistry 

A new species TERP was added to CB05 to represent terpenes. The CB05 TERP chemistry is 

based on the SAPRC99 lumped terpene chemistry (Carter, 2000) translated to CB05 species. 

EXTENDED MECHANISM WITH EXPLICIT SPECIES 

An extended version of CB05 was developed by adding explicit reactions for several organic 

compounds. Explicit chemistry was added for organic compounds that are air toxics and/or 

precursors to secondary organic aerosol. The explicit compounds were added as tracer species 

that are decayed by oxidants (OH, etc.) without perturbing the oxidant levels. This approach 

makes the extended mechanism independent of the core mechanism so that the explicit 

compounds in the extended mechanism could be used in conjunction with any core mechanism 

(e.g., CB05, CB4, SAPRC99). The reactions for the extended organic mechanism are listed in 

Table 2-3. 

Table 2-3. Reactions in the extended CB05 mechanism that may be added to the core 

mechanism. 

Reaction 

Label Reactants Products Rate Expression 

T01 PFRM + OH OH 9.0E-12 

T02 PFRM + NO3 NO3 5.8E-16 

T03 PFRM + O O 3.4E-11 @ 1600 

T04 PFRM 1.0/<HCHO_R_SAPRC99> 

T05 PFRM 1.0/<HCHO_M_SAPRC99> 

T06 PACT + OH OH 5.6E-12 @ -270 

T07 PACT + NO3 NO3 1.4E-12 @ 1900 

T08 PACT + O O 1.8E-11 @ 1100 

T09 PACT 1.0/<CCHO_R_SAPRC99> 

T10 BUTD + OH OH + SACR 1.4E-11 @ -424. 

T11 BUTD + O3 O3 + SACR 8.2E-15 @ 2070. 

T12 BUTD + NO3 NO3 + SACR 1.79E-13 

T13 BUTD + O O3 + SACR 3.99E-12(T/298)**1.45 

T14 PACR + OH OH 2.0E-11 

T15 PACR + O3 O3 2.61E-19 

T16 PACR + NO3 NO3 1.7E-11 @ 3131. 

T17 PACR 1.0/<ACROLEIN_SAPRC99>

T18 SACR + OH OH 2.0E-11 

T19 SACR + O3 O3 2.61E-19 

T20 SACR + NO3 NO3 1.7E-11 @ 3131. 

T21 SACR 1.0/<ACROLEIN_SAPRC99>

T22 TOLU + OH OH 1.8E-12 @ -355. 

T23 MXYL + OH OH 1.7E-11 @ -116. 

T24 OXYL + OH OH 1.22E-11 

T25 PXYL + OH OH 1.3E-11 

T26 APIN + O O 2.79E-11 
December 2005 

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 2-11 

Reaction 

Label Reactants Products Rate Expression 

T27 APIN + OH OH 1.2E-11 @ -440. 

T28 APIN + O3 O3 6.3E-16 @ 580. 

T29 APIN + NO3 NO3 1.2E-12 @ -490. 

T30 BPIN + O O 2.81E-11 

T31 BPIN + OH OH 7.51E-11 

T32 BPIN + O3 O3 1.74E-15 @ 1260. 

T33 BPIN + NO3 NO3 2.81E-11 

Explicit Air Toxics 

The following explicit toxic species are included in the extended mechanism: 

 PFRM = primary formaldehyde 

 PACT = primary acetaldehyde 

 BUTD = 1,3-butadiene 

 PACR = primary acrolein 

 SACR = secondary acrolein from 1,3-butadiene 

The primary formaldehyde and acetaldehyde species allow the contributions of these primary 

aldehydes to be quantified. For example, the species FORM in CB05 is the sum of primary and 

secondary formaldehyde. If PFRM is included in the mechanism, primary formaldehyde is given 

directly by PFRM and secondary formaldehyde is the difference FORM – PFRM. For this 

approach to work, emissions of formaldehyde must be mapped to both PFRM and FORM. This 

does not double count the oxidant formation potential of formaldehyde emissions because the 

PFRM species is oxidant neutral. In this approach, PFRM is a “tracer” species whereas FORM 

is an “active” species. 

The same approach works for distinguishing primary from secondary acetaldehyde by using the 

tracer species PACT and the active species ALD2. 

Acrolein is explicitly apportioned as primary and secondary by the tracer species PACR and 

SACR. SACR is formed in CB05 only by reaction of the BUTD tracer (1,3-butadiene), which is 

expected to be the dominant source of secondary acrolein in the atmosphere. 

The mapping of real compounds to model species for tasks such as emissions processing is 

discussed below. 

Explicit Secondary Organic Aerosol Precursors 

Secondary organic aerosol (SOA) formation is dominated by aromatics and biogenic terpene and 

sesquiterpene emissions (Odum et al., 1997). Aerosol yields can be attached to the 

corresponding lumped species in the CB05 core mechanism (TOL, XYL and TERP) to model 

SOA production. However, including explicit aromatics and terpene species in the extended 

mechanism can permit a more refined treatment of SOA production. The following explicit 

aromatics and terpenes are included in the extended mechanism: 
December 2005 

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 2-12 

 TOLU = toluene 

 MXYL = m-xylene 

 OXYL = o-xylene 

 PXYL = p-xylene 

 APIN = alpha-pinene 

 BPIN = beta-pinene 

The methodology for using the CB05 explicit species to model SOA formation will depend upon 

how SOA formation is implemented in the host air quality model. In general, SOA formation is 

modeled by forming semi-volatile products (SVPs) in VOC reactions. The SVPs are partitioned 

between the gas and aerosol phase according to the ambient conditions (e.g., temperature, preexisting aerosols). Yields of SVPs should be added to the CB05 explicit species reactions in a 

format (i.e., species names and yields) that is compatible with the host air quality model. Data 

on SVP yields are available from Odum et al., 1997 and other studies. 

The explicit aromatic species also may be of interest as air toxics. 

Rate Constant Data 

The rate constant data sources for species in the extended mechanism that are not also in the 

CB05 core mechanism are listed below. 

OH + BUTD. Liu, A., W.A. Mulac, and C.D. Jonah (1992) “Rate constants for the gas phase 

reactions of OH radicals with 1,3 butadiene and allene at 1 atmosphere in Ar and over the 

temperature range 303-1173K” J. Phys. Chem. Vol. 92 

O3 + BUTD. Treacy, J., M. ElHag, D. O'Farrell, and H. Sidebottom (1992) “Reactions of ozone 

with unsaturated organic compounds” Ber. Bunsenges. Phys. Chem., Vol. 96, pp 422-7. 

NO3 + BUTD. Ellermann, T., O.J. Nielsen, and H. Skov (1992) “Absolute rate constents for the 

reactions of NO3 radicals with a series of dienes at 295K” Chem. Phy. Lett., Vol. 200, 

pp. 224-9. 

O3P + BUTD. Adusei, G.Y.; Fontijn, A 1993 “Kinetics of the reaction between O(3P) atoms 

and 1,3-butadiene between 280 and 1015 K” J. Phys. Chem, Vol. 97, pp 1406 – 1408. 

OH + PACR. Orlando, J.J.; Tyndall, G.S. (2002) “Mechanisms for the reactions of OH with 

two unsaturated aldehydes: Crotonaldehyde and acrolein” J. Phys. Chem. A, Vol. 106, pp 

12252 – 12259. 

O3 + PACR. Grosjean, D.; Grosjean, E.; Williams, E.L., II (1993) “Rate constants for the gasphase reactions of ozone with unsaturated alcohols, esters, and carbonyls” Int. J. Chem. 

Kinet Vol 25, pp 783 – 794. 

NO3 + PACR. Cabanas, B.; Salgado, S.; Martin, P.; Baeza, M.T.; Martinez, E. (2001) “Nighttime Atmospheric Loss Process for Unsaturated Aldehydes: Reaction with NO3 

Radicals” J. Phys. Chem. A: Vol. 105, pp 4440 – 4445. 
December 2005 

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 2-13 

OH + OXYL and PXYL. Atkinson, R. and Aschmann S.M (1989) “Rate constants for the gasphase reactions of the OH radical with a series of aromatic hydrocarbons at 296K” Int. J. 

Chem. Kinet., Vol. 21, pp 355-365. 

OH + MXYL. Atkinson, R. (1986) "Kinetics and Mechanisms of the Gas Phase Reactions of 

the Hydroxyl Radical with Organic Compounds", Chem. Rev., Vol. 86, pp 69-201. 

O + APIN and BPIN. Luo, D., J.A. Pierce, I.L. Malkina, and W.P.L. Carter (1996) “Rate 

constants for the reactions of O(3P) with selected monoterpenes” Int. J. Chem. Kinet., 

Vol. 28, pp 1-8. 

OH, O3 and NO3 + APIN. IUPAC (2005) 

OH + BPIN. Foster, P., I. Denis and V. Jacob (1996) “Chap.7: Aerosol surface reactions and 

photocatalysis” in Vol. 2 of Hetreogeneous and Liquid Phase Processess book, pp 191-

196. 

O3 + BPIN. Khamaganor, V.G. and R.A. Hites (2001) “Rate Constants for the Gas-Phase 

Reactions of Ozone with Isoprene, alpha, and beta-Pinene, and Limonene as a Function 

of Temperature” J. Phys. Chem. A., Vol. 105, pp 815-822. 

NO3 + BPIN. Kind, I., T. Berndt and O. Boge (1998) “Gas-phase rate constants for the reaction 

of NO3 radicals with a series of cyclic alkenes, 2-ethyl-1-butene and 2,3-dimethyl-1,3-

butadiene” Chem. Phys. Lett., Vol. 288, pp 111-118. 

REACTIVE CHLORINE CHEMISTRY 

Tanaka et al. (2003) developed an extension to the CB4 mechanism with chlorine chemistry to 

evaluate the potential impact of reactive chlorine emissions (i.e., Cl2 and HOCl) on tropospheric 

ozone formation. The Tanaka chlorine mechanism was reviewed and updated to be compatible 

with CB05. The reactions in Table 2-4 should be added to the CB05 core mechanism for 

modeling reactive chlorine. Table 2-5 identifies the species added for the reactive chlorine 

mechanism. 

Table 2-4. Reactions in the CB05 reactive chlorine mechanism that may be added to the CB05 

core mechanism. 

Reaction 

Label Reactants Products Rate Expression 

CL1 CL2 2 CL 1.0 x <CL2_CB05> 

CL2 HOCL OH + CL 1.0 x <HOCL_CB05> 

CL3 CL + O3 CLO 2.3E-11 @ 200 

CL4 CLO + CLO 0.3 CL2 + 1.4 CL 1.63E-14 

CL5 CLO + NO CL + NO2 6.4E-12 @ -290 

CL6 CLO + HO2 HOCL 2.7E-12 @ -220 

CL7 OH + FMCL CL + CO 5.0E-13 

CL8 FMCL CL + CO + HO2 1.0 x <FMCL_CB05> 

CL9 CL + CH4 HCL + MEO2 6.6E-12 @ 1240 

CL10 CL + PAR HCL + 0.870*XO2 + 0.130*XO2N + 0.110*HO2 + 

0.060*ALD2 - 0.110*PAR + 0.760*ROR + 

0.050*ALDX 

5.0E-11 

CL11 CL + ETHA HCL + 0.991*ALD2 + 0.991*XO2 + 0.009*XO2N + 8.3-11 @ 100 
December 2005 

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 2-14 

Reaction 

Label Reactants Products Rate Expression 

HO2 

CL12 CL + ETH FMCL + 2.000*XO2 + 1.000*HO2 + 1.000*FORM 1.07E-10 

CL13 CL + OLE FMCL + 0.330*ALD2 + 0.670*ALDX + 2.000*XO2 + 

1.000*HO2 - 1.000*PAR 

2.5E-10 

CL14 CL + IOLE 0.300*HCL + 0.700*FMCL + 0.450*ALD2 + 

0.550*ALDX + 0.300*OLE + 0.300*PAR + 

2.000*XO2 + 1.000*HO2 

3.5E-10 

CL15 CL + ISOP 0.15HCL + 1.000*XO2 + 1.000*HO2 + 0.850*FMCL 

+ 1.000*ISPD 

4.3E-10 

CL16 CL + FORM HCL + 1.000*HO2 + 1.000*CO 8.2E-11 @ 34 

CL17 CL + ALD2 HCL + C2O3 7.9-11 

CL18 CL + ALDX HCL + CXO3 1.3E-10 

CL19 CL + MEOH HCL + 1.000*HO2 + 1.000*FORM 5.5-11 

CL20 CL + ETOH HCL + 1.000*HO2 + 1.000*ALD2 8.2-11 @ -45 

Table 2-5. Species added to CB05 by the reactive chlorine mechanism. 

Species 

Name Description 

CL2 Molecular chlorine 

HOCL Hypochlorous acid 

CL Chlorine atom 

CLO Chlorine monoxide 

FMCL Formyl chloride (HC(O)Cl) 

Considerations in updating the reactive chlorine mechanism for CB05 are: 

1. Reaction rate constants were updated from Tanaka et al (2003) using the latest IUPAC 

(2005) recommendations except as described below. 

2. CH4 is added as an explicit species and the Cl + CH4 are products updated to be explicit 

methylperoxy radical. 

3. The Cl + PAR products are updated to be the same as OH + PAR in CB05. The Cl + 

PAR rate is an average over the absolute rates (on a per carbon atom basis) of the alkanes 

listed by in Tanaka et al (2003). 

4. The Cl + OLE rate is updated to an average over the absolute rates (on a per C=C basis) 

for the alkenes presented in Tanaka et al (2003). Reaction products assume that reaction 

with C=C goes by addition and that the Cl atom ends up in a carbonyl compound, 

represented by formyl chloride (HC(O)Cl) as a surrogate. Other carbonyl products are 

ALD2 and ALDX by analogy with OH + OLE reaction. Note that in CB05 there is no 

need to consider H-abstraction from paraffinic carbons adjacent to the C=C group 

because OLE is a 2 carbon species (C=C). 

5. The Cl + IOLE reaction is added. The rate is estimated as the rate for Cl reacting with 

OLE + 2 PAR because IOLE is a 4 carbon species, whereas OLE is a 2 carbon species. 

The products assume that reaction goes 70% by Cl-addition and 30% by H-abstraction, 

consistent with the rate constant assumption. The products for each channel are assumed 

to be: 
December 2005 

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 2-15 

C=C addition => FMCL + 0.65 ALD2 + 0.35 ALDX + 2 XO2 + HO2 

H-abstraction => HCL + ALDX + OLE + XO2 + HO2 

Cl-addition reactions are assumed to form acyl chlorides that are represented by formyl 

chloride (FMCL) as a surrogate, plus aldehydes that are split between ALD2 and ALDX 

by analogy with the OH + IOLE reaction. H-abstraction is assumed to form HCl plus 

unsaturated carbonyls that are represented as ALDX + OLE. 

6. The Cl + isoprene chemistry is extensively revised from Tanaka et al. (2003). The goal 

of Tanaka et al. was to track a unique marker for the CL + ISOP reaction to permit 

comparison with ambient data. The goal for CB05 is to track the fate of the Cl and the 

fate of the carbon in isoprene. The HCl and FMCL yields reflect the balance between Habstraction and addition pathways of 15% and 85% (Personal communication from Dr. 

Renyi Zhang, Texas A&M University: manuscript submitted). FMCL acts as a surrogate 

for the fate of all Cl-addition pathways. The lumped isoprene oxidation product from the 

CB05 mechanism (ISPD) accounts for the carbon containing products. 

7. FMCL (formyl chloride) serves as a surrogate for all products where chlorine is 

incorporated into a chlorocarbonyl after an addition reaction, i.e., for olefins. The 

purpose is to account for sequestration of Cl in an organic molecule (chlorocarbonyl) 

allowing for the Cl to return later as a Cl-atom after the chlorocarbonyl reacts with OH or 

photolyses. 

8. Reactions of Cl-atoms with aldehydes (ALD2 and ALDX) are included with rate 

constants from IUPAC (2005) and products the same as corresponding OH reactions. 

The organic products of Cl + ALDX are uncertain because there may be H-abstraction at 

the paraffinic carbon atoms of higher aldehydes. 

9. No Cl-atom reactions are included for TOL, XYL or TERP because the products are 

uncertain. Omitting these reactions may not greatly alter the fate of Cl-atoms because, 

unlike OH, Cl-atoms react rapidly with all VOCs. For example, the global background 

for methane of ~1.7 ppm provides a significant “universal” sink for Cl-atoms because Clatoms react quite rapidly with methane. 

10. The self-reaction of ClO radicals is added to account for situations where intense sources 

of ClO (e.g., high Cl2 emissions) exceed the availability of NO or HO2 to act as sinks for 

ClO. The products of the CLO self-reaction are highly condensed to approximate the 

final products under tropospheric conditions. 

11. No Cl-atom reaction with NO2 is included because the product CLNO2 photolyses 

rapidly. 

CHEMICAL SPECIES MAPPING FOR CB05 MECHANISMS

An integral part of any condensed chemical mechanism is the assignment from real world 

organic species to the lumped species of the condensed mechanism. The existing chemical 

species mapping for CB4 was updated for CB05. The changes were: 
December 2005 

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 2-16 

1. All assignments to 2 ALD2 representing internal olefins were changed to IOLE. Note 

that internal olefins substituted at the double bond are different, as described next. 

2. All remaining ALD2 assignments were changed to ALDX except for acetaldehyde, 2-

methyl-2-butene and 3-substituted alk-2-enes (which remain assigned to n PAR + 

ALD2). Alkenes that are branched at the double bond are represented as aldehyde + PAR 

because their dominant reaction products (e.g., acetone plus acetaldehyde from 2-methyl2-butene) are less reactive than the IOLE. 

3. Terpenes were mapped to TERP 

A list of mappings from real organic species to CB05 model species is provided in Appendix A. 

The following species mapping changes apply specifically to the extended version of the CB05 

mechanism: 

4. Formaldehyde is mapped to PFRM as well as FORM 

5. Acetaldehyde is mapped to PACT as well as ALD2 

6. 1,3-Butadiene is mapped to BUTD as well as 2 OLE 

7. Acrolein is mapped to PACR as well as 0.5 OLE plus ALDX 

8. Toluene is mapped to TOLU as well as TOL 

 

9. p-Xylene is mapped to PXYL as well as XYL 

10. o-Xylene is mapped to OXYL as well as XYL 

11. m-Xylene is mapped to MXYL as well as XYL 

12. α-Pinene is mapped to APIN as well as TERP 

13. β- Pinene is mapped to APIN as well as TERP 

No changes to species mappings for organic compounds are required for the CB05 reactive 

chlorine mechanism. However, emission inventory preparation for the CB05 reactive chlorine 

mechanism should consider sources of reactive chlorine (CL2 and HOCl). 
December 2005 

H:\EPA_CB4\Report\final\Sec3_Testing.doc 3-1 

3. CB05 IMPLEMENTATION TESTING 

EPA is implementing the CB05 mechanism into the CMAQ air quality model. Tests were 

performed to confirm that the CMAQ implementation is correct. Independent rate constant 

calculations performed by SmogReyes and EPA checked the kinetic rate constant expressions. 

Independent box model simulations by the same groups checked the complete mechanism 

implementation, i.e., the reactions, photolysis data and rate constant data. Box model 

calculations also compared the CB05 mechanism to CB4, and these comparisons are discussed 

first. 

COMPARING CB05 TO CB4 

The CB05 mechanism was implemented in the OZIPM box model for comparison with CB4 as 

shown in Figure 3-1. The version of CB4 compared is the OTAG version of CB4 (discussed in 

Section 1). The scenario modeled is an MIR (maximum incremental reactivity) condition with 

an urban emissions mix of VOCs and NOx. The MIR condition has low VOC/NOx ratio where 

adding VOC has the greatest incremental impact on the ozone production rate. The VOC 

composition used for CB4 and CB05 is compared in Table 3-1 on a moles carbon basis. The 

difference from CB4 to CB05 is that ALD2 is disaggregated to ALD2, IOLE and ALDX. 

Table 3-1. VOC composition used for the box model comparison of CB4 and CB05. 

Fractional Contribution to Moles Carbon 

CB Species CB4 CB05 

PAR 0.675 0.675 

ETH 0.045 0.045 

OLE 0.034 0.034 

TOL 0.116 0.116 

XYL 0.078 0.078 

MEOH 0.001 0.001 

ETOH 0.009 0.009 

ISOP 0.5 0.5 

CRES 0.002 0.002 

FORM 0.009 0.009 

ALD2 0.027 0.006 

IOLE N/A 0.018 

ALDX N/A 0.003 

Total 1.496 1.496 
December 2005 

H:\EPA_CB4\Report\final\Sec3_Testing.doc 3-2 

Figure 3-1. Comparison of CB4 and CB05 ozone predictions for urban MIR conditions. 

CB05 forms ozone more rapidly than CB4 for the MIR condition compared in Figure 3-1, but 

ultimately CB4 and CB05 form the same amount of ozone. The faster ozone formation rate in 

CB05 results from including ALDX (higher aldehydes) and IOLE (internal olefins) in the 

mechanism that boost radical production in the morning. ALDX boosts radical production 

because higher aldehydes produce more radicals than acetaldehyde (i.e., have a higher quantum 

yield for radicals) when they photolyse. IOLE boosts radical production directly via reaction 

products and indirectly because ALDX is a product of IOLE degradation. 

The formation of nitric acid and hydrogen peroxide by CB4 and CB05 is compared in Figures 3-

2 and 3-3 for the MIR condition. Nitric acid formation is similar, but hydrogen peroxide 

production is slower in CB05. However, note that very little hydrogen peroxide is formed by 

either CB05 or CB4 at MIR conditions. Comparing hydrogen peroxide is more meaningful for 

MOR than MIR conditions. CB05 and CB4 also were compared under maximum ozone 

formation (MOIR) box model conditions (Figures 3-4 to 3-6). The VOC compositions for the 

MOR simulations were the same as for the MIR simulations (Table 3-1). The MOIR condition 

differs from the MIR condition in having lower NOx levels, resulting in higher ozone. The 

MOIR VOC/NOx ratio was set for CB4 and not re-adjusted for CB05, so the CB05 result is 

probably not exactly at the MOIR condition. CB05 produced slightly lower final ozone and 

nitric acid than CB4, but slightly higher hydrogen peroxide. CB05 had more rapid initial 

production of ozone, nitric acid and hydrogen peroxide than CB4 due to the ALOX and IOLE 

changes to CB05. 
December 2005 

H:\EPA_CB4\Report\final\Sec3_Testing.doc 3-3 

Figure 3-2. Comparison of CB4 and CB05 HNO3 predictions for urban MIR conditions. 

Figure 3-3. Comparison of CB4 and CB05 H2O2 predictions for urban MIR conditions. 
December 2005 

H:\EPA_CB4\Report\final\Sec3_Testing.doc 3-4 

Figure 3-4. Comparison of CB4 and CB05 ozone predictions for urban MOIR conditions. 

Figure 3-5. Comparison of CB4 and CB05 HNO3 predictions for urban MOIR conditions. 
December 2005 

H:\EPA_CB4\Report\final\Sec3_Testing.doc 3-5 

Figure 3-6. Comparison of CB4 and CB05 H2O2 predictions for urban MOIR conditions. 

RATE CONSTANT COMPARISONS 

The CB05 kinetic rate constant expressions were checked by independent calculations for three 

temperature/pressure conditions: 

 Pressure Temperature (K) 

1 atm 298 

 0.5 atm 298 

 1 atm 310 

Both temperature and pressure were varied because some rate expressions depend upon both 

parameters. Rate constants were compared in units of ppm and minutes, as used within the 

CMAQ air quality model, such that units conversion from the molecular units (molecules per 

cm3

 and seconds) of the rate expressions also was tested. The rate constant comparison (Table 3-

2) found very good agreement for all reactions. The largest difference of 1.2% was for the 

reaction of OH with CO that uses a unique rate expression. 
December 2005 

H:\EPA_CB4\Report\final\Sec3_Testing.doc 3-6 

Table 3-2. Comparison of CB05 thermal rate constants calculated by SmogReyes and EPA for 

three different temperature/pressure conditions (units are ppm and minutes). 

SmogReyes EPA Percent Difference 1

Temperature (K) 298 298 310 298 298 310 298 298 310 

Reaction Pressure (Atm) 1 0.5 1 1 0.5 1 1 0.5 1 

1 NO2 + hv 2 

2 O + O2 + M 2.22E-05 5.55E-06 1.87E-05 2.22E-05 5.55E-06 1.87E-05 0.0% 0.0% 0.2% 

3 O3 + NO 2.89E+01 1.44E+01 3.38E+01 2.89E+01 1.44E+01 3.37E+01 0.0% 0.3% 0.2% 

4 O + NO2 1.51E+04 7.54E+03 1.42E+04 1.51E+04 7.57E+03 1.42E+04 0.2% 0.4% 0.1% 

5 O + NO2 4.85E+03 1.50E+03 4.30E+03 4.85E+03 1.50E+03 4.30E+03 0.1% 0.0% 0.1% 

6 O + NO 2.46E+03 6.74E+02 2.18E+03 2.46E+03 6.74E+02 2.18E+03 0.0% 0.0% 0.2% 

7 NO2 + O3 4.76E-02 2.38E-02 6.30E-02 4.77E-02 2.38E-02 6.30E-02 0.2% 0.0% 0.1% 

8 O3 + hv 2 

9 O3 + hv 2

10 O1D + M 4.37E+04 2.19E+04 4.15E+04 4.37E+04 2.19E+04 4.15E+04 0.0% 0.2% 0.1% 

11 O1D + H2O 3.25E+05 1.63E+05 3.12E+05 3.25E+05 1.63E+05 3.13E+05 0.0% 0.3% 0.2% 

12 O3 + OH 1.07E+02 5.36E+01 1.16E+02 1.07E+02 5.36E+01 1.16E+02 0.2% 0.0% 0.2% 

13 O3 + HO2 2.85E+00 1.43E+00 2.92E+00 2.85E+00 1.43E+00 2.92E+00 0.1% 0.2% 0.0% 

14 NO3 + hv 2 

15 NO3 + hv 2

16 NO3 + NO 3.92E+04 1.96E+04 3.69E+04 3.92E+04 1.96E+04 3.69E+04 0.1% 0.1% 0.1% 

17 NO3 + NO2 9.70E-01 4.85E-01 1.10E+00 9.70E-01 4.85E-01 1.10E+00 0.0% 0.0% 0.2% 

18 NO3 + NO2 1.74E+03 8.08E+02 1.60E+03 1.74E+03 8.08E+02 1.60E+03 0.1% 0.0% 0.1% 

19 N2O5 + H2O 3.70E-07 1.85E-07 3.56E-07 3.69E-07 1.85E-07 3.55E-07 0.1% 0.1% 0.2% 

20 N2O5 + H2O + H2O 6.55E-11 1.64E-11 6.06E-11 6.55E-11 1.64E-11 6.05E-11 0.0% 0.1% 0.1% 

21 N2O5 3.17E+00 2.85E+00 1.31E+01 3.17E+00 2.85E+00 1.31E+01 0.1% 0.1% 0.1% 

22 NO + NO + O2 7.11E-10 1.78E-10 6.13E-10 7.11E-10 1.78E-10 6.14E-10 0.0% 0.1% 0.1% 

23 NO + NO2 + H2O 1.82E-11 4.55E-12 1.68E-11 1.82E-11 4.55E-12 1.68E-11 0.0% 0.0% 0.1% 

24 NO + OH 1.09E+04 3.60E+03 9.69E+03 1.09E+04 3.60E+03 9.69E+03 0.4% 0.1% 0.1% 

25 HONO + hv 2 

26 OH + HONO 7.19E+03 3.59E+03 7.27E+03 7.19E+03 3.59E+03 7.27E+03 0.0% 0.1% 0.0% 

27 HONO + HONO 1.48E-05 7.39E-06 1.42E-05 1.48E-05 7.39E-06 1.42E-05 0.1% 0.0% 0.1% 

28 NO2 + OH 1.55E+04 5.56E+03 1.38E+04 1.55E+04 5.56E+03 1.38E+04 0.3% 0.1% 0.2% 

29 OH + HNO3 2.28E+02 1.13E+02 1.95E+02 2.28E+02 1.13E+02 1.95E+02 0.0% 0.1% 0.1% 

30 HO2 + NO 1.20E+04 5.99E+03 1.11E+04 1.20E+04 5.98E+03 1.11E+04 0.2% 0.1% 0.4% 

31 HO2 + NO2 2.05E+03 7.10E+02 1.81E+03 2.05E+03 7.10E+02 1.81E+03 0.2% 0.0% 0.1% 

32 PNA 4.99E+00 3.50E+00 2.02E+01 4.99E+00 3.50E+00 2.02E+01 0.1% 0.0% 0.1% 

33 OH + PNA 6.88E+03 3.44E+03 6.29E+03 6.88E+03 3.44E+03 6.29E+03 0.0% 0.0% 0.0% 

34 HO2 + HO2 4.32E+03 1.72E+03 3.70E+03 4.32E+03 1.72E+03 3.70E+03 0.0% 0.2% 0.1% 

35 HO2 + HO2 + H2O 2.39E-01 4.76E-02 1.48E-01 2.39E-01 4.76E-02 1.48E-01 0.2% 0.1% 0.2% 

36 H2O2 + hv 2 

37 OH + H2O2 2.51E+03 1.25E+03 2.46E+03 2.51E+03 1.25E+03 2.46E+03 0.2% 0.2% 0.0% 

38 O1D + H2 1.63E+05 8.13E+04 1.56E+05 1.63E+05 8.13E+04 1.56E+05 0.3% 0.0% 0.2% 

39 OH + H2 9.89E+00 4.95E+00 1.23E+01 9.89E+00 4.95E+00 1.23E+01 0.0% 0.1% 0.2% 

40 OH + O 4.86E+04 2.43E+04 4.60E+04 4.86E+04 2.43E+04 4.60E+04 0.1% 0.1% 0.1% 

41 OH + OH 2.77E+03 1.39E+03 2.75E+03 2.77E+03 1.39E+03 2.75E+03 0.2% 0.2% 0.0% 

42 OH + OH 9.30E+03 3.14E+03 8.57E+03 9.30E+03 3.14E+03 8.57E+03 0.0% 0.1% 0.0% 

43 OH + HO2 1.64E+05 8.20E+04 1.53E+05 1.64E+05 8.21E+04 1.53E+05 0.0% 0.1% 0.1% 

44 HO2 + O 8.68E+04 4.34E+04 8.13E+04 8.67E+04 4.34E+04 8.12E+04 0.1% 0.0% 0.1% 

45 H2O2 + O 2.51E+00 1.26E+00 3.14E+00 2.52E+00 1.26E+00 3.14E+00 0.3% 0.3% 0.0% 

46 NO3 + O 1.48E+04 7.39E+03 1.42E+04 1.48E+04 7.39E+03 1.42E+04 0.1% 0.0% 0.1% 

47 NO3 + OH 3.25E+04 1.63E+04 3.13E+04 3.25E+04 1.63E+04 3.13E+04 0.0% 0.3% 0.1% 
December 2005 

H:\EPA_CB4\Report\final\Sec3_Testing.doc 3-7 

SmogReyes EPA Percent Difference 1

Temperature (K) 298 298 310 298 298 310 298 298 310 

Reaction Pressure (Atm) 1 0.5 1 1 0.5 1 1 0.5 1 

48 NO3 + HO2 5.17E+03 2.59E+03 4.97E+03 5.17E+03 2.59E+03 4.97E+03 0.1% 0.1% 0.0% 

49 NO3 + O3 1.48E-02 7.39E-03 1.42E-02 1.48E-02 7.39E-03 1.42E-02 0.1% 0.0% 0.1% 

50 NO3 + NO3 3.38E-01 1.69E-01 4.47E-01 3.38E-01 1.69E-01 4.46E-01 0.1% 0.1% 0.2% 

51 PNA + hv 2 

52 HNO3 + hv 2 

53 N2O5 + hv 2 

54 XO2 + NO 1.31E+04 6.54E+03 1.20E+04 1.31E+04 6.54E+03 1.20E+04 0.2% 0.0% 0.1% 

55 XO2N + NO 1.31E+04 6.54E+03 1.20E+04 1.31E+04 6.54E+03 1.20E+04 0.2% 0.0% 0.1% 

56 XO2 + HO2 1.16E+04 5.81E+03 1.02E+04 1.16E+04 5.81E+03 1.02E+04 0.1% 0.1% 0.2% 

57 XO2N + HO2 1.16E+04 5.81E+03 1.02E+04 1.16E+04 5.81E+03 1.02E+04 0.1% 0.1% 0.2% 

58 XO2 + XO2 1.01E+02 5.03E+01 9.66E+01 1.00E+02 5.02E+01 9.66E+01 0.5% 0.1% 0.0% 

59 XO2N + XO2N 1.01E+02 5.03E+01 9.66E+01 1.00E+02 5.02E+01 9.66E+01 0.5% 0.1% 0.0% 

60 XO2 + XO2N 1.01E+02 5.03E+01 9.66E+01 1.00E+02 5.02E+01 9.66E+01 0.5% 0.1% 0.0% 

61 NTR + OH 2.60E+02 1.30E+02 2.62E+02 2.61E+02 1.30E+02 2.62E+02 0.2% 0.2% 0.1% 

62 NTR + hv 2 

63 ROOH + OH 8.42E+03 4.21E+03 7.89E+03 8.42E+03 4.21E+03 7.89E+03 0.0% 0.0% 0.1% 

64 ROOH + hv 2 

65 OH + CO 3.55E+02 1.44E+02 3.41E+02 3.56E+02 1.44E+02 3.37E+02 0.4% 0.1% 1.2% 

66 OH + CH4 9.38E+00 4.69E+00 1.14E+01 9.37E+00 4.69E+00 1.13E+01 0.1% 0.0% 0.5% 

67 MEO2 + NO 1.13E+04 5.66E+03 1.05E+04 1.13E+04 5.66E+03 1.05E+04 0.2% 0.0% 0.3% 

68 MEO2 + HO2 7.51E+03 3.75E+03 6.55E+03 7.51E+03 3.75E+03 6.55E+03 0.0% 0.1% 0.1% 

69 MEO2 + MEO2 5.20E+02 2.60E+02 4.75E+02 5.20E+02 2.60E+02 4.75E+02 0.1% 0.1% 0.0% 

70 MEPX + OH 1.10E+04 5.49E+03 1.03E+04 1.10E+04 5.49E+03 1.03E+04 0.1% 0.1% 0.0% 

71 MEPX + hv 2 

72 MEOH + OH 1.35E+03 6.74E+02 1.40E+03 1.35E+03 6.74E+02 1.40E+03 0.2% 0.1% 0.2% 

73 FORM + OH 1.33E+04 6.65E+03 1.28E+04 1.33E+04 6.65E+03 1.28E+04 0.0% 0.0% 0.1% 

74 FORM + hv 2 

75 FORM + hv 2

76 FORM + O 2.34E+02 1.17E+02 2.77E+02 2.34E+02 1.17E+02 2.77E+02 0.0% 0.0% 0.0% 

77 FORM + NO3 8.57E-01 4.29E-01 8.24E-01 8.57E-01 4.29E-01 8.24E-01 0.0% 0.1% 0.0% 

78 FORM + HO2 1.17E+02 5.84E+01 1.03E+02 1.17E+02 5.84E+01 1.03E+02 0.2% 0.0% 0.5% 

79 HCO3 9.05E+03 9.05E+03 2.25E+04 9.05E+03 9.05E+03 2.25E+04 0.0% 0.0% 0.1% 

80 HCO3 + NO 8.28E+03 4.14E+03 7.96E+03 8.28E+03 4.14E+03 7.96E+03 0.0% 0.0% 0.0% 

81 HCO3 + HO2 1.86E+04 9.30E+03 1.33E+04 1.86E+04 9.30E+03 1.33E+04 0.0% 0.0% 0.2% 

82 FACD + OH 5.91E+02 2.96E+02 5.68E+02 5.91E+02 2.96E+02 5.68E+02 0.0% 0.1% 0.0% 

83 ALD2 + O 6.63E+02 3.32E+02 7.35E+02 6.63E+02 3.32E+02 7.36E+02 0.1% 0.1% 0.1% 

84 ALD2 + OH 2.05E+04 1.02E+04 1.90E+04 2.05E+04 1.02E+04 1.90E+04 0.1% 0.4% 0.0% 

85 ALD2 + NO3 3.52E+00 1.76E+00 4.33E+00 3.52E+00 1.76E+00 4.33E+00 0.1% 0.1% 0.0% 

86 ALD2 + hv 2 

87 C2O3 + NO 2.96E+04 1.48E+04 2.75E+04 2.96E+04 1.48E+04 2.75E+04 0.1% 0.1% 0.1% 

88 C2O3 + NO2 1.55E+04 7.50E+03 1.42E+04 1.55E+04 7.49E+03 1.42E+04 0.1% 0.1% 0.0% 

89 PAN 1.99E-02 1.93E-02 1.19E-01 1.99E-02 1.93E-02 1.19E-01 0.2% 0.1% 0.4% 

90 PAN + hv 2 

91 C2O3 + HO2 2.08E+04 1.04E+04 1.75E+04 2.08E+04 1.04E+04 1.75E+04 0.2% 0.2% 0.0% 

92 C2O3 + MEO2 1.58E+04 7.91E+03 1.43E+04 1.58E+04 7.91E+03 1.43E+04 0.2% 0.1% 0.3% 

93 C2O3 + XO2 2.36E+04 1.18E+04 1.97E+04 2.36E+04 1.18E+04 1.97E+04 0.1% 0.1% 0.1% 

94 C2O3 + C2O3 2.30E+04 1.15E+04 2.07E+04 2.29E+04 1.15E+04 2.07E+04 0.2% 0.2% 0.1% 

95 PACD + OH 1.16E+03 5.78E+02 1.08E+03 1.16E+03 5.78E+02 1.08E+03 0.3% 0.1% 0.3% 

96 PACD + hv 2 
December 2005 

H:\EPA_CB4\Report\final\Sec3_Testing.doc 3-8 

SmogReyes EPA Percent Difference 1

Temperature (K) 298 298 310 298 298 310 298 298 310 

Reaction Pressure (Atm) 1 0.5 1 1 0.5 1 1 0.5 1 

97 AACD + OH 1.16E+03 5.78E+02 1.08E+03 1.16E+03 5.78E+02 1.08E+03 0.3% 0.1% 0.3% 

98 ALDX + O 1.04E+03 5.18E+02 1.12E+03 1.04E+03 5.18E+02 1.12E+03 0.3% 0.1% 0.1% 

99 ALDX + OH 2.93E+04 1.47E+04 2.67E+04 2.93E+04 1.47E+04 2.68E+04 0.1% 0.2% 0.3% 

100 ALDX + NO3 9.61E+00 4.80E+00 9.24E+00 9.61E+00 4.80E+00 9.23E+00 0.0% 0.1% 0.1% 

101 ALDX + hv 2 

102 CXO3 + NO 3.10E+04 1.55E+04 2.85E+04 3.10E+04 1.55E+04 2.85E+04 0.0% 0.0% 0.0% 

103 CXO3 + NO2 1.55E+04 7.50E+03 1.42E+04 1.55E+04 7.49E+03 1.42E+04 0.1% 0.1% 0.0% 

104 PANX 1.99E-02 1.93E-02 1.19E-01 1.99E-02 1.93E-02 1.19E-01 0.2% 0.1% 0.4% 

105 PANX + hv 2 

106 PANX + OH 4.43E+02 2.22E+02 4.26E+02 4.43E+02 2.22E+02 4.26E+02 0.1% 0.1% 0.0% 

107 CXO3 + HO2 2.08E+04 1.04E+04 1.75E+04 2.08E+04 1.04E+04 1.75E+04 0.2% 0.2% 0.0% 

108 CXO3 + MEO2 1.58E+04 7.91E+03 1.43E+04 1.58E+04 7.91E+03 1.43E+04 0.2% 0.1% 0.3% 

109 CXO3 + XO2 2.36E+04 1.18E+04 1.97E+04 2.36E+04 1.18E+04 1.97E+04 0.2% 0.2% 0.2% 

110 CXO3 + CXO3 2.30E+04 1.15E+04 2.07E+04 2.29E+04 1.15E+04 2.07E+04 0.2% 0.2% 0.1% 

111 CXO3 + C2O3 2.30E+04 1.15E+04 2.07E+04 2.29E+04 1.15E+04 2.07E+04 0.2% 0.2% 0.1% 

112 PAR + OH 1.20E+03 5.99E+02 1.15E+03 1.20E+03 5.99E+02 1.15E+03 0.2% 0.1% 0.1% 

113 ROR 1.32E+05 1.32E+05 3.72E+05 1.32E+05 1.32E+05 3.72E+05 0.3% 0.3% 0.0% 

114 ROR 9.60E+04 9.60E+04 9.60E+04 9.60E+04 9.60E+04 9.60E+04 0.0% 0.0% 0.0% 

115 ROR + NO2 2.22E+04 1.11E+04 2.13E+04 2.22E+04 1.11E+04 2.13E+04 0.1% 0.1% 0.1% 

116 O + OLE 5.78E+03 2.89E+03 5.76E+03 5.78E+03 2.89E+03 5.76E+03 0.1% 0.1% 0.0% 

117 OH + OLE 4.73E+04 2.36E+04 4.55E+04 4.73E+04 2.36E+04 4.55E+04 0.0% 0.2% 0.1% 

118 O3 + OLE 1.63E-02 8.13E-03 2.01E-02 1.64E-02 8.18E-03 2.01E-02 0.9% 0.6% 0.2% 

119 NO3 + OLE 7.36E-01 3.68E-01 9.37E-01 7.36E-01 3.68E-01 9.37E-01 0.0% 0.0% 0.0% 

120 O + ETH 1.08E+03 5.39E+02 1.15E+03 1.08E+03 5.39E+02 1.15E+03 0.2% 0.0% 0.1% 

121 OH + ETH 1.20E+04 5.90E+03 1.16E+04 1.20E+04 5.90E+03 1.16E+04 0.4% 0.1% 0.3% 

122 O3 + ETH 2.61E-03 1.30E-03 3.53E-03 2.61E-03 1.30E-03 3.52E-03 0.2% 0.2% 0.3% 

123 NO3 + ETH 3.10E-01 1.55E-01 4.33E-01 3.10E-01 1.55E-01 4.33E-01 0.1% 0.1% 0.0% 

124 IOLE + O 3.40E+04 1.70E+04 3.27E+04 3.40E+04 1.70E+04 3.27E+04 0.0% 0.0% 0.0% 

125 IOLE + OH 9.36E+04 4.68E+04 8.38E+04 9.36E+04 4.68E+04 8.38E+04 0.0% 0.0% 0.0% 

126 IOLE + O3 3.10E-01 1.55E-01 3.44E-01 3.10E-01 1.55E-01 3.43E-01 0.1% 0.1% 0.2% 

127 IOLE + NO3 5.73E+02 2.87E+02 5.71E+02 5.73E+02 2.87E+02 5.71E+02 0.1% 0.1% 0.1% 

128 TOL + OH 8.76E+03 4.38E+03 8.04E+03 8.76E+03 4.38E+03 8.04E+03 0.0% 0.0% 0.0% 

129 TO2 + NO 1.20E+04 5.99E+03 1.15E+04 1.20E+04 5.99E+03 1.15E+04 0.2% 0.1% 0.3% 

130 TO2 2.52E+02 2.52E+02 2.52E+02 2.52E+02 2.52E+02 2.52E+02 0.0% 0.0% 0.0% 

131 OH + CRES 6.06E+04 3.03E+04 5.83E+04 6.06E+04 3.03E+04 5.82E+04 0.0% 0.0% 0.1% 

132 CRES + NO3 3.25E+04 1.63E+04 3.12E+04 3.25E+04 1.63E+04 3.13E+04 0.0% 0.3% 0.2% 

133 CRO + NO2 2.07E+04 1.03E+04 1.99E+04 2.07E+04 1.03E+04 1.99E+04 0.0% 0.4% 0.0% 

134 CRO + HO2 8.13E+03 4.06E+03 7.82E+03 8.13E+03 4.06E+03 7.81E+03 0.0% 0.1% 0.1% 

135 OPEN + hv 2 

136 OPEN + OH 4.43E+04 2.22E+04 4.26E+04 4.43E+04 2.22E+04 4.26E+04 0.1% 0.1% 0.0% 

137 OPEN + O3 1.49E-02 7.45E-03 1.53E-02 1.49E-02 7.45E-03 1.53E-02 0.0% 0.0% 0.1% 

138 OH + XYL 3.70E+04 1.85E+04 3.50E+04 3.71E+04 1.85E+04 3.51E+04 0.4% 0.1% 0.2% 

139 OH + MGLY 2.66E+04 1.33E+04 2.56E+04 2.66E+04 1.33E+04 2.56E+04 0.0% 0.0% 0.1% 

140 MGLY + hv 2 

141 O + ISOP 5.32E+04 2.66E+04 5.11E+04 5.32E+04 2.66E+04 5.11E+04 0.0% 0.0% 0.1% 

142 OH + ISOP 1.47E+05 7.37E+04 1.34E+05 1.47E+05 7.37E+04 1.34E+05 0.3% 0.0% 0.0% 

143 O3 + ISOP 1.90E-02 9.50E-03 2.34E-02 1.90E-02 9.50E-03 2.34E-02 0.0% 0.0% 0.1% 

144 NO3 + ISOP 9.96E+02 4.98E+02 1.02E+03 9.96E+02 4.98E+02 1.01E+03 0.0% 0.0% 0.5% 

145 OH + ISPD 4.97E+04 2.48E+04 4.77E+04 4.97E+04 2.48E+04 4.77E+04 0.1% 0.1% 0.1% 
December 2005 

H:\EPA_CB4\Report\final\Sec3_Testing.doc 3-9 

SmogReyes EPA Percent Difference 1

Temperature (K) 298 298 310 298 298 310 298 298 310 

Reaction Pressure (Atm) 1 0.5 1 1 0.5 1 1 0.5 1 

146 O3 + ISPD 1.05E-02 5.25E-03 1.01E-02 1.05E-02 5.25E-03 1.01E-02 0.1% 0.1% 0.1% 

147 NO3 + ISPD 1.48E+00 7.39E-01 1.42E+00 1.48E+00 7.39E-01 1.42E+00 0.1% 0.0% 0.1% 

148 ISPD + hv 2 

149 TERP + O 5.32E+04 2.66E+04 5.11E+04 5.32E+04 2.66E+04 5.11E+04 0.0% 0.0% 0.1% 

150 TERP + OH 1.00E+05 5.00E+04 9.07E+04 1.00E+05 5.00E+04 9.07E+04 0.0% 0.0% 0.0% 

151 TERP + O3 1.13E-01 5.64E-02 1.21E-01 1.13E-01 5.64E-02 1.21E-01 0.2% 0.0% 0.1% 

152 TERP + NO3 9.84E+03 4.92E+03 9.25E+03 9.84E+03 4.92E+03 9.24E+03 0.0% 0.0% 0.1% 

153 SO2 + OH 1.31E+03 5.11E+02 1.20E+03 1.31E+03 5.11E+02 1.20E+03 0.3% 0.0% 0.3% 

154 OH + ETOH 4.71E+03 2.36E+03 4.67E+03 4.71E+03 2.36E+03 4.67E+03 0.1% 0.1% 0.0% 

155 OH + ETHA 3.55E+02 1.77E+02 3.92E+02 3.55E+02 1.77E+02 3.92E+02 0.1% 0.2% 0.0% 

156 NO2 + ISOP 2.22E-04 1.11E-04 2.13E-04 2.22E-04 1.11E-04 2.13E-04 0.1% 0.1% 0.1% 

Maximum Difference 0.9% 0.6% 1.2% 

Table Notes 

1. Differences are calculated as the absolute difference between SmogReyes and EPA values 

divided by the EPA value. 

2. Photolysis reactions (with a reactant hv) are not compared. 

BOX MODEL COMPARISONS

Comparing the results of box model simulations checked the CMAQ implementation of the 

CB05 mechanism reactions together with photolysis data and rate constant data. SmogReyes 

implemented CB05 in the OZIPM box model and set up calculations for the three temperature 

and pressure conditions as were used for the rate constant comparison shown in Table 3-2. EPA 

set up a box model version of CMAQ to match as closely as possible the conditions of the 

OZIPM tests. There was generally good agreement between the concentrations predicted by the 

two box models suggesting that the mechanism implementation was correct in both models. 

Example comparisons for 298 K and 1 atmosphere are shown in Figure 3-7 (NO, NO2 and O3) 

and Figure 3-8 (HONO and HO2). Figures 3-9 and 3-10 show similar comparisons at different 

temperatures and pressures. These comparisons confirm that CB05 is implemented correctly in 

the CMAQ model. 
December 2005 

H:\EPA_CB4\Report\final\Sec3_Testing.doc 3-10 

Figure 3-7. Comparison of results from the CMAQ and OZIPM box models for NO, NO2 and O3

at 298 K and 1 atmosphere. 

Figure 3-8. Comparison of results from the CMAQ and OZIPM box models for HONO and HO2

at 298 K and 1 atmosphere. 
December 2005 

H:\EPA_CB4\Report\final\Sec3_Testing.doc 3-11 

Figure 3-9. Comparison of results from the CMAQ and OZIPM box models for NO, NO2 and O3

at 298 K and 0.5 atmosphere. 

Figure 3-10. Comparison of results from the CMAQ and OZIPM box models for NO, NO2 and 

O3 at 310K and 1 atmosphere. 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-1 

4. MECHANISM EVALUATION 

UNC CHAMBER 

The University of North Carolina (UNC) operates a smog chamber facility as described in the 

CB4-2002 report (Jeffries, Voicu and Sexton; 2002). For this project, UNC provided a database 

of chamber experiments along with software (called Morpho) to simulate chamber experiments 

and assistance in using the data and software. The CB05 mechanism was implemented in the 

Morpho software and simulation results were compared to experimental data as shown below 

and in Appendix B. 

Updated UNC Wall Reaction Mechanism 

The chemical mechanism used to simulate a chamber experiment must include reactions for both 

the gas-phase chemistry taking place in the chamber and the effects of the chamber walls. 

Chamber walls can provide both sources and sinks for reactive species. The role of the chamber 

walls is most apparent in experiments that are sensitive to input of radicals and/or reactive 

nitrogen species from the chamber walls, such as experiments with carbon monoxide (CO). 

Jeffries, Voicu and Sexton (2002) revised the UNC chamber mechanism in the process of 

developing the CB4-2002. Nonetheless, the chamber characterization experiments from CB4-

2002 still show biases for ozone and nitrogen species as shown in CO experiments in Figures 4-1 

and 4-2 (from Jeffries, Voicu and Sexton; 2002). We reviewed and updated the chamber wall 

mechanism, as described below, to improve performance in chamber characterization 

experiments before beginning the evaluation of the CB05 mechanism. The improvement in the 

wall reaction mechanism can be seen in Figures 4-1 and 4-2 by comparing the CB05 (top) and 

CB4-2002 (bottom) simulations. Results of additional UNC chamber characterization 

experiments with CB05 are included in Appendix B. 

The wall mechanism developed by Jeffries, Voicu and Sexton (2002) was modified in four ways: 

(1) The deposition rate of N2O5 was increased by a factor of 9 in order to more accurately 

simulate the observed NO2 data in experiments with only NOx and high CO. These 

experiments have essentially no PAN that normally might confound the data analysis. 

(2) Radicals from wall nitrous acid (HONO) photolysis were changed from a mechanism 

using N2O4 on the walls to a mechanism based on NO, NO2, and water on the walls. 

(3) A pathway releasing NO2 from nitric acid on the walls (WHNO3) was added. 

(4) Loss of PNA (HO2NO2) to the walls was added. This loss primarily impacts the highest 

CO experiments. 

The original Jeffries, Voicu and Sexton (2002) wall reactions and the revised reactions used in 

this study are compared in Tables 4-1 and 4-2. 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-2 

Table 4-1. Wall reactions from the Jeffries, Voicu and Sexton (2002) UNC chamber 

mechanisms that were changed for this project. 

Label Reactants Products Rate Expression 

W1 N2O5 + WH2O 2.0 * WHNO3 2.6E-18 

W2 NO2 + H2O WNO2 1.0E-22 

W3 WNO2 NO2 6.6E-7 

W4 WNO2+WNO2 WN2O4 1.0E-10 

W5 WN2O4 + WH2O WHONO + WHNO3 1.0E-14 

Table 4-2. New wall reactions for the UNC chamber used in this project. 

Label Reactants Products Rate Expression 

W1 N2O5 + WH2O 2.0 * WHNO3 2.34E-17 

W2 NO2 + H2O WNO2 1.0E-23 

W3 WNO2 NO2 1.0E-4 

W4 NO + H2O WNO 1.5E-23 

W5 WNO NO 1.0E-4 

W6 WNO+WNO2 2.0 * WHONO 2.0E-14 

W7 WHNO3 NO2 5.0E-6 

W8 PNA + WH2O WHNO3 1.0E-17 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-3 

Figure 4-1. Comparison of CB05 (top) and CB4-2002 (bottom) simulations of UNC carbon 

monoxide experiment August 30, 1993 (red). 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-4 

Figure 4-2. Comparison of CB05 (top) and CB4-2002 (bottom) simulations of UNC carbon 

monoxide experiment August 30, 1996 (blue). 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-5 

ALDX Mechanism Update 

One of the CB05 updates discussed in Section2 is the inclusion of a higher aldehyde species in 

addition to acetaldehyde. The impact of adding a higher aldehyde species (ALDX) to CB05 can 

be seen in performance for UBC chamber experiments for aldehydes larger than acetaldehyde. 

Figure 4-3 compares the performance of CB05 and CB4-2002 in simulating an experiment from 

September 4, 1997 (red chamber) with trimethylacetaldehyde and propionaldehyde. CB4-2002 

represents these aldehydes using ALD2 and produces ozone too slowly, although the final ozone 

level is simulated quite well. CB05 produces ozone more rapidly because of greater radical 

production from ALDX photolysis than ALD2 photolysis. The rate of NO to NO2 conversion 

also is simulated better by CB05 than CB4-2002. 

Figure 4-3. Comparison of CB05 (top) and CB4-2002 (bottom) simulations of UNC experiment 

of September 4, 1997 (red chamber) with trimethylacetaldehyde and propionaldehyde. 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-6 

Including ALDX in CB05 also improves performance for olefins larger than propene. For 

example propionaldehyde is a product of 1–butene reactions and butyraldehyde is a product of 1-

pentene reactions. Figure 4-4 compares CB05 and CB4-2002 performance for an experiment 

from October 16, 1996 (blue chamber) with propene, 1-butene and 1-pentene. The rate of ozone 

production and the rate of NO to NO2 conversion are simulated much better by CB05 using 

ALDX than by CB4-2002 using ALD2 to represent the aldehyde products of olefin reactions. 

Figure 4-4. Comparison of CB05 (top) and CB4-2002 (bottom) simulations of UNC experiment 

October 16, 1996 (blue chamber) with propene, 1-butene and 1-pentene. 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-7 

IOLE Mechanism Update 

Including IOLE in CB05 also improves performance for internal olefins (i.e., RHC=CHR) 

compared to the CB4 surrogate representation of 2 ALD2. Figure 4-5 compares CB05 and CB4-

2002 performance for an experiment from September 14, 1996 (blue chamber) with an equimolar 

mixture of all butene isomers (1-butene, cis-2-butene, trans-2-butene, isobutene). CB05 does 

better than CB4-2002 in simulating the rate of ozone production, the final ozone level and the 

rate of NO to NO2 conversion. CB05 produces ozone more rapidly because of radical production 

from IOLE reactions and formation of ALDX as a product in addition to ALD2. 

Figure 4-5. Comparison of CB05 (top) and CB4-2002 (bottom) simulations of UNC experiment 

September 14, 1996 (blue chamber) with an equimolar mixture of all butene isomers (1-butene, 

cis-2-butene, trans-2-butene, isobutene).
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-8 

Summary of CB05 Performance for UNC Chamber Experiments 

Results of CB05 simulations for UNC chamber experiments are shown in Appendix B. 

Experiments are grouped according to the VOC introduced into the red chamber. Each 

experiment is identified by date and chamber (red or blue) and further details on each experiment 

are given in Jeffries, Voicu and Sexton (2002). 

The performance of CB05 against the UNC chamber data is summarized as follows: 

Chamber Background. The chamber background experiments mostly reflect the wall mechanism 

and performed well. 

Carbon monoxide. The CO experiments reflect the wall mechanism and core inorganic chemistry 

in CB05 and performed well with a couple of exceptions that are not understood. 

Formaldehyde. The formaldehyde experiments test formaldehyde and basic radical chemistry. 

CB05 performed very well. 

Methane. Methane experiments are somewhat sensitive to the chamber wall mechanism and any 

impurity in the methane because methane has very low reactivity. CB05 performed well 

with a couple of exceptions that are not understood 

Acetaldehyde (ALD2). Acetaldehyde experiments add PAN formation and additional radical 

reactions to the chemistry tested by methane and formaldehyde experiments. CB05 

performed well for experiments with acetaldehyde and acetaldehyde mixtures. 

Higher aldehydes (ALDX). CB05 performed well for experiments with higher aldehyde 

mixtures. As discussed above, ALDX is an area of improvement in CB05 over CB4. 

Ethene (ETH). Ethene experiments test ethene and formaldehyde chemistry. CB05 performed 

quite well for ethene experiments. 

Terminal olefins (OLE). Terminal olefins test the OLE chemistry for alk-1-enes and rely upon 

ADLX, ALD2 and formaldehyde chemistry. CB05 performed quite well for OLE 

experiments. 

Olefin mixtures (IOLE and OLE). Internal olefins test the IOLE chemistry for alk-2-enes and 

similar compounds and rely upon ADLX, ALD2 and formaldehyde chemistry. CB05 

performed well for IOLE experiments. 

Alkanes (PAR). Alkane experiments test the PAR chemistry in addition to the aldehyde and 

inorganic chemistry. CB05 over predicted ozone in one butane experiments but not 

others. CB05 performed well for alkanes higher than butane. 

Aromatics (TOL and XYL). Aromatics chemistry is complex and includes several species 

specific to aromatics, but also relies upon simpler aldehyde chemistry. CB05 

performance showed more scatter for aromatics than other species. CB05 generally 

under-predicted the initial rise in ozone and the peak ozone, but did not show a clear 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-9 

trend toward over or under prediction of the final ozone formation. This result differs 

from the UCR chamber evaluation presented below. 

Isoprene. Isoprene is an explicit species in CB05 that involves the aldehyde and basic inorganic 

chemistry. CB05 tended to under predict ozone formation in isoprene experiments. This 

result is surprising as the isoprene chemistry was not overtly changed from the previous 

CB4 mechanisms (e.g., CB4-2002). The current CB05 isoprene mechanism was 

implemented as a translation of the SAPRC one-product isoprene mechanism. This 

should be revisited, possibly by implementing a “three product” mechanism with 

methacorlein and methylvinyl ketone as explicit products (Carter 1996). 

Urban Mixtures. CB05 tended to under predict ozone formation in many but not all experiments 

with the UNC synthetic urban mixture. Further investigation would be needed to 

understand this performance. 

UCR CHAMBER

The University of California at Riverside (UCR) operates several smog chambers including a 

new chamber (the “EPA chamber”), described by Carter et al., 2005, which is capable of 

experiments at lower NOx levels than the earlier chambers. Dr. Carter of UCR performed 

chamber simulations to evaluate both the CB05 and the SAPRC99 “fixed parameter” 

mechanisms (Carter, 2000) for this study. Results from several simulations in the EPA chamber 

are shown in Figures 4-6 to 4-15. The results are summarized as follows. CB05 and SAPRC99 

performance was similar for experiments with CO, formaldehyde and ethene. CB05 performed 

somewhat better than SAPRC99 for propene although both mechanisms performed quite well. 

CB05 and SAPRC99 performance was similar and good for butane. 

The CB05 and SAPRC99 fixed parameter version (Carter, 2000) were compared against 

experiments from several chambers at UCR. Dr. Carter at UCR performed the UCR chamber 

simulations for both CB05 and SAPRC99 and provided the results to the CB05 mechanism 

developers. 

Over 350 UCR experiments for individual compounds and compound mixtures were used to 

evaluate the mechanisms as listed in Tables 4-3 and 4-4. Each group of experiments was 

compared by displaying the bias in predicted oxidant production (O3-NO) with experiment time, 

as seen in Figure 4-16. The bias values (prediction minus observation divided by observation) 

are assigned to ranges (bins) and counted. Good performance is shown by most of the counts 

being in the bins with low bias. Separate lines are shown for each hour of the experiment (1 to 6 

hours) to reveal biases in the rate of oxidant production (early hours) versus biases in the final 

amount of oxidant (late hours). 

Different compounds test different parts of the photochemical mechanisms, as discussed above 

in the evaluation against UNC chamber data. Compounds are ordered in Figure 4-16 and the 

discussion below so as to involve progressively more of the mechanism in the evaluation. 

Carbon Monoxide (CO). The CO experiments were used by UCR to adjust the chamber wall 

mechanism for CB05. The UCR chamber wall mechanisms differ by chamber and were 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-10 

not reevaluated in detail for CB05. A single parameter that controls the production of 

radicals by wall reactions was adjusted (upward) for CB05 compared to SAPRC99. 

Formaldehyde. CB05 showed a slight under-prediction bias for formaldehyde in contrast to 

SAPRC99, which showed neutral bias. This may be related to differences in the OH plus 

NO2 rate constant between CB05 and SAPRC99 (CB05 rate is slightly higher). Note that 

CB05 and SAPRC99 are using the same photolysis data for formaldehyde so this is not a 

factor in the different performance of the two mechanisms. 

Acetaldehyde. Both mechanisms performed well for acetaldehyde with CB05 performing 

exceptionally well. 

Ethene. CB05 and SAPRC99 performance for ethene was similar with both mechanisms 

showing a slight positive bias. The similarity in CB05 and SAPRC99 performance for 

ethane is surprising given the difference in performance for formaldehyde (see above) 

because ethene experiments are very sensitive to the formaldehyde mechanism. 

Propene. Both CB05 and SAPRC99 tended to under-predict oxidant production for propene in 

the UCR chambers, especially in the early experiment hours. CB05 had less underprediction of the final oxidant levels from propene than SAPRC99. 

Trans-2-butene. This compound tests the new IOLE chemistry in CB05. CB05 performed very 

well for trans-2-butene. SAPRC99 tended to under-estimate the initial oxidant 

production rate but then performed similar to CB05 in predicting the final oxidant levels. 

Isoprene. CB05 and SAPRC99 performed similarly and well for isoprene with near zero bias 

being the most frequent performance. CB05 had a slightly broader bias distribution than 

SAPRC99. This may be because SAPRC99 has a more complex “3-product” mechanism 

than the CB05 “1-product” mechanism. The CB05 1-product mechanism is a translation 

of the SAPRC 1-product mechanism. 

n-Butane. CB05 had a narrower and negative bias distribution whereas SAPRC99 had a broader 

and positive bias distribution for n-butane. For both mechanisms, near-zero bias was the 

most frequent outcome for the final oxidant levels in n-butane experiments. 

n-Octane. Both CB05 and SAPRC99 tended to under-predict oxidant production from n-octane, 

with greater negative bias for SAPRC99 than CB05. 

Toluene. CB05 under-predicted the initial rate of oxidant formation from toluene but tended to 

produce the right final oxidant levels. SAPRC99 tended to slightly under-predict the 

initial oxidant production rate but slightly over-predict the final oxidant levels for 

toluene. Thus, SAPRC99 has closer to zero overall bias for toluene than CB05. 

m-Xylene. CB05 tended to under-predict the initial rate of oxidant formation from m-xylene and 

slightly under-predict the final oxidant levels. SAPRC99 performance for m-xylene was 

very good and most often showed zero bias for oxidant levels throughout experiments. 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-11 

o-Xylene. Both CB05 and SAPRC99 showed a lot of scatter in oxidant bias for o-xylene. CB05 

had less scatter and tended to under-predict the final oxidants whereas SAPRC99 had 

more scatter and tended to over-predict the final oxidant levels for o-xylene. 

1,2,4-Trimethylbenzene. Both CB05 and SAPRC99 showed scattered oxidant bias for 1,2,4-

Trimethylbenzene. CB05 tended to under-predict the final oxidants whereas SAPRC99 

tended to over-predict the final oxidant levels for 1,2,4-trimethylbenzene. 

Alpha-pinene and beta-pinene. The new CB05 terpene mechanism is a translation of the 

SAPRC99 lumped terpene mechanism, so CB05 and SAPRC99 are expected to show 

similar performance for alpha- and beta-pinene, as was the case. Performance for alphapinene was much better than for beta-pinene illustrating the difficulty in representing 

oxidant formation from both species using a single lumped terpene mechanism. 

Surrogate mixtures. Oxidant performance was evaluated for two different types of multi-species 

mixtures (surrogate mixtures) employed at UCR that are referred to as the “EPA 

Surrogate” and the “Full Surrogate.” CB05 and SAPRC99 performance for surrogate 

mixtures is quite similar. For the “EPA Surrogate” experiments, both mechanisms show 

scattered negative bias with a greater tendency to under-predict the early oxidant 

production rate and lesser bias for the final oxidant levels. The assessment for the “Full 

Surrogate” runs is similar except that the CB05 bias is less scattered and marginally 

closer to neutral than SAPRC99. Overall, CB05 shows less scatter but SAPRC99 has 

marginally less negative bias than CB05 for the final oxidant levels in surrogate mixture 

experiments. Neither mechanism performed clearly better than the other in the surrogate 

mixture experiments. 

The area of most difference between CB05 and SAPRC99 is aromatics chemistry. The 

SAPRC99 aromatics chemistry performs much better than CB05 against the UCR chamber data 

CB05 predicts less ozone formation from aromatics than SAPRC99, especially for toluene, and 

therefore systematically under predicts the UCR chamber ozone in aromatics experiments. 

CB05 showed less tendency to under predict ozone in UNC aromatics chamber experiments than 

UCR experiments. There appears to be a systematic difference in the aromatics experiments 

between the UCR and UNC chambers that may be related to the chambers or the design of the 

experiments. This could be investigated by evaluating the SAPRC99 mechanism against UNC 

chamber experiments. Further work is warranted to understand differences in the UCR and UNC 

aromatics experiments and differences between the aromatics mechanisms. 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-12 

Table 4-3. Compounds and numbers of UCR experiments included in the comparison between 

CB05 and SAPRC99 mechanism performance. 

Compound Number of Experiments 

Carbon monoxide 18 

Formaldehyde 24 

Acetaldehyde 12 

Ethene 39 

Propene 89 

t-2-Butene 12 

Isoprene 18 

Butane 10 

Octane 5 

Toluene 28 

m-Xylene 27 

o-Xylene 13 

123-trimethylbenzene 9 

Alpha-Pinene 11 

Beta-Pinene 9 

EPA surrogate mixture 25 

Full surrogate mixture 18 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc Table 4-4. Numbered UCR chamber experiments used to evaluate the CB05 and SAPRC99 mechanisms, by cCO 

Formaldehyde Acet- aldehyde Ethene Propene trans-2- Butene Isoprene Butane Octane Toluene m-Xylene o-Xylene 

1,2,3-trimethylbenzene a-Pinene 

18 24 12 39 89 12 18 10 5 28 27 13 9 11 CTC031 ITC1549 DTC150A ITC1555 ETC440 XTC081 EC146 ITC511 ETC484 EPA114B ITC534 DTC073A DTC207A DTC201A ETC420 CTC061 ITC1554 DTC150B ITC926 ETC449 XTC082 EC147 ITC811 ETC488 EPA095A ITC699 DTC188A DTC207B DTC203A ETC443 CTC090A ITC864 DTC152B ITC936 DTC026A XTC097 EC157 ITC812 ETC094 EPA083B ITC828 DTC188B DTC208A DTC203B ETC444 CTC090B ETC378 DTC387B ETC220 DTC026B XTC113 ETC493 DTC053A ETC097 EPA085B DTC042A DTC189A DTC208B DTC204A ETC446 EPA057A ETC441 XTC083 ETC221 DTC128A CTC012 ETC501 DTC053B ETC135 EPA113B DTC042B DTC189B DTC209A DTC204B ETC447 EPA057B DTC149A XTC092 ETC381 DTC128B CTC018 ETC307 DTC056A ETC224 DTC151A DTC191A DTC209B CTC056 XTC095 EPA058A DTC149B CTC014 ETC439 DTC129A CTC023 ETC309 DTC056B ETC389 DTC155A DTC191B CTC038 CTC091B OTC318A EPA058B DTC218A CTC015 ETC464 DTC129B CTC049 DTC043B XTC093 ETC393 DTC158A DTC192A CTC039 CTC093A ETC508 EPA061A DTC218B CTC032 ETC466 DTC205A CTC059 DTC021B XTC101 DTC019B DTC170A DTC192B CTC046 CTC093B DTC045B EPA061B DTC270A CTC072 ETC467 DTC205B CTC078 DTC069A EC520 DTC031A XTC106 DTC193A CTC068 DTC044A EPA070A DTC270B EC164 ETC469 DTC246A CTC083A DTC041A EC522 CTC026 DTC193B CTC081 DTC034B EPA070B DTC387A EC254 ETC471 DTC288A CTC083B DTC033A EC524 CTC034 CTC029 CTC091A EPA071A XTC086 ETC473 DTC288B CTC086A EC527 CTC048 CTC035 EC288 EPA071B CTC016 ETC476 DTC301A CTC086B EC669 CTC065 CTC036 EPA103A CTC024 ETC479 DTC301B CTC115A OTC309A CTC079 CTC066 EPA103B CTC077 ETC482 DTC331A CTC115B OTC309B EC264 CTC080 EPA140A CTC095A ETC486 DTC331B CTC132A OTC316A EC266 CTC094A EPA140B CTC095B ETC497 DTC346A CTC132B OTC316B EC269 CTC094B  CTC116A ETC505 DTC346B CTC147A EC270 ETC196  CTC116B DTC041B DTC371A CTC147B EC271 ETC207  CTC133A DTC043A DTC371B CTC153A EC273 ETC301  CTC133B DTC044B DTC393A CTC153B EC293 DTC025A  CTC176A DTC045A DTC393B CTC163A EC327 DTC068B  CTC176B DTC046B DTC405A CTC163B EC340 DTC035A  DTC047A DTC405B CTC170A OTC299A DTC067B  DTC048B DTC417A CTC170B OTC299B CTC109A  DTC050A DTC417B CTC191A OTC300A CTC128A  DTC051A DTC431A CTC191B OTC300B  DTC072B DTC431B CTC203A  XTC105 DTC443A CTC203B  XTC112 DTC443B CTC219A  EC142 DTC458A CTC219B  EC143 DTC458B CTC234A  EC156 DTC472A CTC234B  EC285 DTC472B CTC245A  EC286 DTC483A CTC245B  EC287 DTC483B CTC264A  EPA073A DTC503A CTC264B  EPA073B DTC503B OTC272A  DTC526A OTC272B  DTC526B OTC295A  DTC578A OTC295B  DTC578B OTC298A  DTC597A OTC298B  DTC597B 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-14 

Carbon Monoxide 

SAPRC99 CB05 

Figure 4-6. SAPRC99 (left) and CB05 (right) simulation of a carbon monoxide experiment in 

the EPA chamber at UCR.
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-15 

SAPRC99 

Figure 4-7. SAPRC99 simulation of four formaldehyde experiments in the EPA chamber at 

UCR. 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-16 

CB05 

Figure 4-8. CB05 simulation of four formaldehyde experiments in the EPA chamber at UCR. 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-17 

SAPRC99 CB05 

Figure 4-9. SAPRC99 (left) and CB05 (right) simulation of an ethene experiment in the EPA 

chamber at UCR.

SAPRC99 CB05 

Figure 4-10. SAPRC99 (left) and CB05 (right) simulation of a propene experiment in the EPA 

chamber at UCR.
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-18 

SAPRC99 CB05 

Figure 4-11. SAPRC99 (left) and CB05 (right) simulation of a butane experiment in the EPA 

chamber at UCR.
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-19 

SAPRC99 

Figure 4-12. SAPRC99 simulation of two toluene experiments in the EPA chamber at UCR. 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-20 

CB05 

Figure 4-13. CB05 simulation of two toluene experiments in the EPA chamber at UCR. 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-21 

SAPRC99 

Figure 4-14. SAPRC99 simulation of two xylene experiments in the EPA chamber at UCR. 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-22 

CB05 

Figure 4-15. CB05 simulation of two xylene experiments in the EPA chamber at UCR. 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-23 

CB05 SAPRC99 

Figure 4-16. Bias in oxidant production (O3-NO) at hours 1-6 in UCR chamber experiments for 

the CB05 and SAPRC99 mechanisms, by compound. 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-24 

CB05 SAPRC99 

Figure 4-16. (continued). Bias in oxidant production (O3-NO) at hours 1-6 in UCR chamber 

experiments for the CB05 and SAPRC99 mechanisms, by compound. 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-25 

CB05 SAPRC99 

Figure 4-16. (continued). Bias in oxidant production (O3-NO) at hours 1-6 in UCR chamber 

experiments for the CB05 and SAPRC99 mechanisms, by compound. 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-26 

CB05 SAPRC99 

Figure 4-16. (continued). Bias in oxidant production (O3-NO) at hours 1-6 in UCR chamber 

experiments for the CB05 and SAPRC99 mechanisms, by compound. 
December 2005 

H:\EPA_CB4\Report\final\Sec4_Eval.doc 4-27 

CB05 SAPRC99 

Figure 4-16. (concluded). Bias in oxidant production (O3-NO) at hours 1-6 in UCR chamber 

experiments for the CB05 and SAPRC99 mechanisms, by compound.
December 2005 

H:\EPA_CB4\Report\final\Sec5_SumRec.doc 5-1 

5. SUMMARY AND RECOMMENDATIONS 

The Carbon Bond mechanism has been updated for use in EPA atmospheric modeling studies. 

The starting point for this study was version 4 of the Carbon Bond mechanism (CB4) developed 

in the late 1980s (Gery et al., 1989) as updated in the mid 1990s for EPA’s “OTAG” ozone 

transport assessment study. The new version of the Carbon Bond mechanism is called CB05 

because it was developed in 2005. 

The CB05 is a condensed mechanism of atmospheric oxidant chemistry that provides a basis for 

computer modeling studies of ozone, particulate matter (PM), visibility, acid deposition and air 

toxics issues. Updates in CB05 compared to earlier CB4 mechanisms are: 

• Updated rate constants based on recent (2003 – 2005) IUPAC and NASA evaluations. 

• An extended inorganic reaction set for urban to remote tropospheric conditions. 

• NOx recycling reactions to represent the fate of NOx over multiple days. 

• Explicit organic chemistry for methane and ethane. 

• Explicit methylperoxy radical, methyl hydroperoxide and formic acid. 

• Lumped higher organic peroxides, organic acids and peracids. 

• Internal olefin (R-HC=CH-R) species called IOLE. 

• Higher aldehyde species ALDX making ALD2 explicitly acetaldehyde. 

• Higher peroxyacyl nitrate species from ALDX called PANX. 

• Lumped terpene species called TERP. 

• Optional mechanism extension for reactive chlorine chemistry. 

• Optional extended mechanism with explicit reactions for air-toxics. 

The core CB05 mechanism has 51 species and 156 reactions. The CB05 was evaluated against 

smog chamber data from the Universities of North Carolina (UNC) and California at Riverside 

(UCTR). An updated wall reaction mechanism was developed for the UNC chamber that 

improved performance in experiments that are sensitive to chamber radical sources. The 

addition of higher aldehyde (ALDX) and internal olefin (IOLE) species to CB05 improved 

mechanism performance for simulating these species groups. The addition of organic peroxide 

species improves the simulation of oxidants that are involved in PM sulfate formation. The 

addition of explicit methylperoxy radical improves the simulation of hydrogen peroxide under 

low NOx conditions. 

Two CB05 mechanism extensions were developed. The optional reactive chlorine chemistry 

mechanism can be used in conjunction with the CB05 core mechanism to model the impact of 

Cl2 and/or HOCl emissions on oxidant formation and VOC decay rates. The optional explicit 

species extension can be used in conjunction with the CB05 (or another) core mechanism to 

model the following toxic species: primary formaldehyde, primary acetaldehyde, 1,3-butadiene, 

primary and secondary acrolein. Other optional explicit species are toluene, o-xylene, m-xylene, 

p-xylene, apha-pinene and beta-pinene. These include the main precursors to secondary organic 

aerosol (SOA) and could be used as the basis for refined modeling approach for SOA that is 

independent of the core mechanism selected (e.g., CB4, CB05 or SAPRC99). 
December 2005 

H:\EPA_CB4\Report\final\Sec5_SumRec.doc 5-2 

Recommendations

• Terpene experiments from UNC should be implemented in the UNC “Morpho” chamber 

simulation software and used to evaluate, and possibly update, the CB05 terpene 

mechanism. 

• The SAPRC99 mechanism should be evaluated against UNC chamber experiments using 

the Morpho software and updated UNC chamber wall mechanisms. 

• There should be a comparative study of UCR and UNC chamber experiments, especially 

for aromatics, to understand apparent chamber differences. 
December2005 

H:\EPA_CB4\Report\final\References.doc R-1 

REFERENCES 

Adelman Z.E., 1999. “A Reevaluation Of The Carbon Bond-IV Photochemical Mechanism.” 

School of Public Health,University of North Carolina, Chapel Hill, North Carolina, 

Canosa-Mas, C.E., S.J. Smith, S.J. Waygood, and R.P. Wayne. 1991. “Study of the temperature 

dependence of the reaction of the nitrate radical with propene.” J. Chem. Soc. Faraday 

Trans., 87, 3473-3478. 

Carter, W.P.L. 2000. “Programs and Files Implementing the SAPRC-99 Mechanism and its 

Associated Emissions Processing Procedures for Models-3 and Other Regional Models.” 

January. http://pah.cert.ucr.edu/~carter/SAPRC99.htm 

Carter W. P. L. 1996. “Condensed atmospheric photooxidation mechanisms for isoprene.” 

Atmospheric Environment, 30, 4275-4290. 

Carter, W. P. L., and R. Atkinson. 1996. “Development and evaluation of a detailed mechanism 

for the atmospheric reactions of isoprene and NOx.” Int. J. Chem. Kinet, 28, 497-530. 

Carter, W. P. L., D.R. Cocker III, D. R. Fitz, I.L. Malkina, K. Bumiller, C. G. Sauer, J.T. Pisano, 

C. Bufalino, and C. Song. 2005. “A new environmental chamber for evaluation of gasphase chemical mechanisms and secondary aerosol formation.” Accepted for publication 

in Atmospheric Environment, July 15, 2005. 

Cvetanovic, R.J. 1987. “Evaluated chemical kinetic data for the reactions of atomic oxygen 

O(3P) with unsaturated hydrocarbons.” J. Phys. Chem. Ref. Data, 16, 261. 

Dodge, M.C. 1991. “Updating of the CB4 Mechanism.” Memorandum to Shao-Hang Chu, 

Environmental Protection Agency, Office of Air Quality Planning and Standards, 

Research Triangle Park, NC. March. 

Gery, M.W., G.Z. Whitten, J.P. Killus, and M.C. Dodge. 1989. “A Photochemical Kinetics 

Mechanism for Urban and Regional Scale Computer Modeling.” J. Geophys. Res., 94, 

925-956. 

Herron, J.T. 1988 “Evaluated chemical kinetic data for the reactions of atomic oxygen O(3P) 

with saturated organic compounds in the gas phase” J. Phys. Chem. Ref. Data, 17, 967. 

Hjorth, J., J. Notholt, and G. Restelli 1992 “A spectroscopic study of the equilibrium NO2 + 

NO3 + M = N2O5 + M and the kinetics of the O3/N2O5/NO3/NO2/air system” Int. J. 

Chem. Kinet., 24, 51-65. 

IUPAC. 2005. R. Atkinson, D.L. Baulch, R.A. Cox, J.N. Crowley, R.F. Hampson, R.G. Hynes, 

M.E. Jenkin, J.A. Kerr, M.J. Rossi, and J. Troe. “Evaluated kinetic and photochemical 

data for atmospheric chemistry - IUPAC subcommittee on gas kinetic data evaluation for 

atmospheric chemistry.” July 2005 web version available from http://www.iupackinetic.ch.cam.ac.uk/index.html 
December2005 

H:\EPA_CB4\Report\final\References.doc R-2 

Jeffries, H.E., I. Voicu, and K. Sexton. 2002. “Experimental Tests of Reactivity and Reevaluation of The Carbon Bond Four Photochemical Reaction Mechanism.” Final report 

for Cooperative Agreement No. R828906, U.S. EPA, RTP, NC. 

Kaiser, E.W. and C.H. Wu. 1977. “A Kinetic study of the Gas Phase Formation and 

Decomposition Reactions of Nitrous Acid.” J. Phys Chem. 81, 1701-1706. 

Ligocki, M. P. and G. Z. Whitten. 1992. “Modeling of Air Toxics with the Urban Airshed 

Model.” Presented at the Air and Waste Management Association 85th Annual Meeting 

and Exhibition, Kansas City, Missouri. Paper 92-84.12. 

Ligocki, M.P., R.R. Schulhof, R.E. Jackson, M.M. Jimenez, G.Z. Whitten, G.M. Wilson, T.C. 

Myers, and J.L. Fieber. 1992. “Modeling the Effects of Reformulated Gasolines on 

Ozone and Toxics Concentrations in the Baltimore and Houston Areas,” Final Report to 

U.S. EPA, Systems Applications International, San Rafael, CA. 

Luo, D., J.A. Pierce, J.L. Malkina, and W.P.L. Carter. 1996. “Rate Constants for the Reactions 

of O(3P) with Selected Monoterpenes.” Int. J. Chem. Kinet., 28, 1-8. 

Morris, R. E. and T. C. Myers. 1990. “User's Guide for the Urban Airshed Model. Volume I: 

User's Manual for UAM (CB-IV).” Prepared for the U.S. Environmental Protection 

Agency (EPA-450/4-90-007a), Systems Applications International, San Rafael, CA. 

NASA/JPL 2003. S.P. Sander, R.R. Friedl, D. M. Golden, M. J. Kurylo, R. E. Huie, V. L. Orkin, 

G. K. Moortgat, A. R. Ravishankara, C. E. Kolb, M. J. Molina, and B. J Finlayson-Pitts. 

Chemical Kinetics and Photochemical Data for use in Atmospheric Studies, Evaluation 

Number 14. NASA Jet Propulsion Laboratory. February. Available from 

http://jpldataeval.jpl.nasa.gov/download.html. 

Novelli, P.C., P.M. Lang, K.A. Masarie, D.F. Hurst, R. Myers, and J.W. Elkins. 1999. 

“Molecular hydrogen in the troposphere: global distribution and budget.” J. Geophys. 

Res. 104, 30,427-30,444. 

Odum, J.R., T.P.W. Jungkamp, R.J. Griffin, R.C. Flagan and J.H. Seinfeld. 1997. “The 

Atmospheric Aerosol-Forming Potential of Whole Gasoline Vapor.” Science, 276, 96-99. 

See also Environmental Science & Technology, 31, 1890-1897. 

Tanaka P.L., D.T. Allen, E.C. McDonald-Buller, S. Chang, Y. Kimura, G. Yarwood and J.D. 

Neece. 2003. “Development of a chlorine mechanism for use in the carbon bond IV 

chemistry model.” Journal of Geophysical Research. Vol. 108(D4), 4145. 

Troe J., 2001. “Analysis of the temperature and pressure dependence of the reaction HO + NO2 

+ M → HONO2 + M.” Int. J. Chem. Kinet., 33, 878-889. 

Tuazon, E.C, W.P.L. Carter, and R. Atkinson. 1991. “Thermal decomposition of peroxyacetyl 

nitrate and reactions of acetyl peroxy radicals with NO and NO2 over the temperature 

range 283-313 K.” J. Phys. Chem., 95, 2434-2437. 
December2005 

H:\EPA_CB4\Report\final\References.doc R-3 

Tyndall, G.S., R.A. Cox, C. Granier, R. Lesclaux, G.K. Moortgat, M.J. Pilling, A.R. 

Ravishankara, T.J. Wallington. 2001. “Atmospheric chemistry of small organic peroxy 

radicals.” Journal of Geophysical Research, 106(D11), 12157-12182. 

Wahner A., T.F. Mentel, and M. Sohn. 1998. “Gas-phase reaction of N2O5 with water vapor: 

importance of heterogeneous hydrolysis of N2O5 and surface desorption of HNO3 in a 

large teflon chamber.” Geophysical Research Letters, 25, 2169-2172. 

Whitten, G.Z. and H. Hogo. 1986. “Guidelines for Using OZIPM-4 with CBM-4 or Optional 

Mechanisms. Volume 2: Computer Code.” Report prepared for the U.S. Environmental 

Protection Agency. 

Whitten, G.Z. et al. 1986. “Guidelines for Using OZIPM-4 with CBM-4 or Optional 

Mechanisms. Volume 1: Description of the Ozone Isopleth Plotting Package, Version 

4.” Report prepared for the U.S. Environmental Protection Agency. 

Whitten, G.Z., H.P. Duel, C.S. Burton and J.L. Haney. 1996. “Overview of the implementation 

of an updated isoprene chemistry mechanism in CB4/UAM-V.” Memorandum from 

Systems Application International, San Rafael, CA. June. 

Yarwood, G. and S. Burton. 1993. “An update to the radical-radical termination reactions in the 

CBM-IV.” Memorandum from Systems Application International, San Rafael, CA. 

December. 

Yarwood G., P. D. Maker and H. Niki. 1991. “Kinetic and IR spectroscopic studies of formyl 

bromide (HCOBr) formed via the reaction HCO + Br2 --> HCOBr + Br.” J. Phys. 

Chem., 95(12), 4773-4777. 

Yarwood G., N. Peng and H. Niki. 1992. “FTIR study of the Cl and Br atom initiated oxidation 

of ethane.” Int. J. Chem. Kinet., 24:369. 

Yarwood, G., N. Peng and H. Niki. 1991. “FTIR study of the mechanism of the Cl and Br atom 

initiated oxidation of acetylene.” J. Phys. Chem., 95(19), 7330-7337. 

Yarwood, G., G. Z. Whitten and S. Rao. 2005. “Updates to the Carbon Bond 4 Photochemical 

Mechanism.” Report prepared for the Lake Michigan Air Directors Consortium, Des 

Plains, IL. 

Zaveri, R.A., L.K. Peters. 1999. “A new lumped structure photochemical mechanism for largescale applications.” Journal of Geophysical Research, 104, 30,387-30,400. 
Appendix A 

Assignments from VOC Species to CB05 Model Species 
Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Species

name NASN PA

R OLE TOL

XYL FORM

ALD2 ETH ISOP MEOH ETOH NR CH4 ETH

A IOLE

ALKANES - examplesmethane 000000000000100

propane 0 1.5 0 0 0 0 0 0 0 0 0 1.5 0 0 0 ethane 000000000000010

n-butane 040000000000000

2,2-dimethylpropane 040000000001000

2-methylpropane; isobutane 040000000000000

2-methylpropane; isobutane 040000000000000

n-pentane 050000000000000

2-methyl-butane 050000000000000

2,2-dimethylbutane 050000000001000

isomers of pentane 050000000000000

cyclopentane 050000000000000

c5 paraffin 050000000000000

dimethylbutane 0 5.75 000000000 0.25 000

isomers of hexane 0 5.83 000000000 0.17 000

2,3-dimethylbutane 060000000000000

cyclohexane 060000000000000

1,6-Diisocyanatohexane 060000000002000

2-methylpentane 060000000000000

3-methylpentane 060000000000000

methylcyclopentane 060000000000000

methylpentane 060000000000000

3,3-dimethylpentane 060000000001000n-hexane 060000000000000

dimethylpentane 0 6.75 000000000 0.25 000

c7 paraffins 0 6.81 000000000 0.19 000

isomers of heptane 0 6.81 000000000 0.19 000

n-octane 070000000001000c7 cycloparaffins 070000000000000

methyl hexane 070000000000000n-decane 070000000003000n-heptane 070000000000000methylcyclohexane 070000000000000

2,4-dimethylpentane 0700000000000002,2,4-trimethylpentane 0700000000010002,3-dimethylpentane 0700000000000002,3,3-trimethylpentane 070000000001000dimethylcyclopentane 070000000000000

ethylcyclopentane 070000000000000

n-nonane 0700000000020002-methylhexane 0700000000000002,2-dimethylhexane 0700000000010003-methylhexane 070000000000000trimethylpentane 0 7.33 000000000 0.67 000

isomers of octane (c8 paraffin) 0 7.62 000000000 0.38 000

Page 1 of 15
Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Species

name NASN PA

R OLE TOL

XYL FORM

ALD2 ETH ISOP MEOH ETOH NR CH4 ETH

A IOLE

methylnonane 0 7.75 000000000 2.25 000

dimethylhexanes 0 7.83 000000000 0.17 000

c8 cycloparaffins 0800000000000003-methylheptane 0800000000000002-methylheptane 0800000000000004-methylheptane 080000000000000methylheptane 080000000000000n-undecane 080000000003000n-dodecane 080000000004000ethylcyclohexane 080000000000000cis-1,4-dimethylcyclohexane 0800000000000002,3,4-trimethylpentane 080000000000000cis-1-methyl-3-ethylcyclopentane 080000000000000isopropylcyclopentane 080000000000000trimethylcyclopentane 080000000000000c8 alkyl cyclohexanes 080000000000000dimethylcyclohexanes 0800000000000002,2,4-trimethylhexane 0800000000010002,4-dimethylhexane 0800000000000002,5-dimethylhexane 0800000000000002,3-dimethylhexane 080000000000000ethylhexane 0800000000000002,2,5-trimethylhexane 080000000001000cis-bicyclo[3.3.0]octane 080000000000000

aliphatics 0 8.08 000000000 0.62 000

diethylcyclohexane 0 8.5 0 0 0 0 0 0 0 0 0 1.5 0 0 0 

isomers of nonane (c9 paraffin) 0 8.75 000000000 0.25 000

trimethylhexanes 0 8.8 0 0 0 0 0 0 0 0 0 0.2 0 0 0 

propenylcyclohexane 071000000000000methyloctanes 090000000000000c9 cycloparaffins 090000000000000methyldodecanes 0900000000040002,4-dimethylheptane 0900000000000003,5-dimethylheptane 0900000000000002,5-dimethylheptane 0900000000000002,3-dimethylheptane 090000000000000ethylheptane 090000000000000ethylbicycloheptane 090000000000000dimethylheptanes 0900000000000002-methyloctane 0900000000000003-methyloctane 0900000000000004-methyloctane 090000000000000propylcyclohexane 0900000000000001,1,3-trimethylcyclohexane 090000000000000ethyldimethylpentane 090000000000000tetramethylcyclopentane 090000000000000c9 alkyl cyclohexanes 090000000000000

Page 2 of 15
Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Species

name NASN PA

R OLE TOL

XYL FORM

ALD2 ETH ISOP MEOH ETOH NR CH4 ETH

A IOLE

ethylmethylcyclohexanes 0900000000000002,3,5-trimethylhexane 090000000000000ethylmethylhexane 090000000000000n-tridecane 090000000004000isopropylcyclohexane (2-methylethyl cycloh 090000000000000Bicyclo[4.3.0]nonane (octahydroindene) 090000000000000unk c9 paraffin 090000000000000methylcyclooctane 090000000000000isomers of decane (c10 paraffins) 0 9.25 000000000 0.75 000

c6 substituted cyclohexane 0 9.33 000000000 2.67 000

isomers of undecane (c11 paraffins) 0 9.5 0 0 0 0 0 0 0 0 0 1.5 0 0 0 

methyldecanes 0 9.5 0 0 0 0 0 0 0 0 0 1.5 0 0 0 

dimethyloctanes 0 10 0000000000000

n-tetradecane 0 10 0000000004000

n-pentadecane 0 10 0000000005000

isomers of tridecane (c13 paraffins) 0 10 0000000003000

2,4,5-trimethylheptane 0 10 0000000000000

methylethylheptane 0 10 0000000000000

trimethylheptanes 0 10 0000000000000

ethyloctane 0 10 0000000000000

2,4-dimethyloctane 0 10 0000000000000

3,4-dimethyloctane 0 10 0000000000000

2,3-dimethyloctane 0 10 0000000000000

2,6-dimethyloctane 0 10 0000000000000

dimethylethylcyclohexane 0 10 0000000000000

isopropylmethylcyclohexane 0 10 0000000000000

butylcyclohexane 0 10 0000000000000

cyclopentylcyclopentane 0 10 0000000000000

c10 alkyl cyclohexanes 0 10 0000000000000

methyl propylcyclohexanes 0 10 0000000000000

tetramethylhexane 0 10 0000000000000

decalins (mixed cis,trans) 0 10 0000000000000

c5 substituted cyclohexane 0 10.25 000000000 0.75 000

dimethylnonanes 0 10.4 0 0 0 0 0 0 0 0 0 0.6 0 0 0 

isomers of dodecane (c12 paraffins) 0 10.67 000000000 1.33 000

isomers of tetradecane (c14 paraffins) 0 10.75 000000000 3.25 000

trimethyloctanes 0 11 0000000000000

hexadecane 0 11 0000000005000

n-heptadecane 0 11 0000000006000

c16 branched alkanes 0 11 0000000005000

dimethylundecanes 0 11 0000000002000

ethylmethyloctane 0 11 0000000000000

n-pentylcyclohexane 0 11 0000000000000

ethyl propylcyclohexanes 0 11 0000000000000

diethylmethylcyclohexanes 0 11 0000000000000

dimethyldecane 0 11 0000000001000

2-methyldecane 0 11 0000000000000

Page 3 of 15
Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Species

name NASN PA

R OLE TOL

XYL FORM

ALD2 ETH ISOP MEOH ETOH NR CH4 ETH

A IOLE

methyldecalins 0 11 0000000000000

methylundecane 0 11.2 0 0 0 0 0 0 0 0 0 0.8 0 0 0 

isomers of pentadecane (c15 paraffins) 0 11.25 000000000 3.75 000

ethyldimethyloctane 0 12 0000000000000

dimethylbutylcyclohexane 0 12 0000000000000

c2 alkyl decalin 0 12 0000000000000

nonadecane 0 13 0000000006000

trimethyldecane 0 13 0000000000000

methylpropylnonane 0 13 0000000000000

eicosane 0 14 0000000006000

isomers of heptadecane (c17 paraffins) 0 15 0000000002000

isomers of octadecane (c18 paraffins) 0 16.5 0 0 0 0 0 0 0 0 0 1.5 0 0 0 

ALKENES - examplesethylene 000000010000000

propylene 011000000000000

1,2-propadiene 0 0 1.5 000000000000

trans-2-butene 000000000000001

cis-2-butene 000000000000001

2-methylpropene (isobutene) 030001000000000

isomers of butene 0 1 0.5 000000000000

1-butene 021000000000000

4-vinylcyclohexene 0210000000000001,2-butadiene {methylallene} 0 1 1.5 000000000000

1,3-butadiene 002000000000000

methylbutene 0 3.33 0.33 0 0 0.33 000000000 

1,3-cyclopentadiene 00000000000000 1.25 methylbutadiene 000000001000000

isoprene 000000001000000

trans-2-pentene 010000000000001

cis-2-pentene 010000000000001

2-methyl-2-butene 030000100000000

2-methyl-1-butene 040001000000000

isomers of pentene 0 2.4 0.2 0 0 0.2 000000000

3-methyl-1-butene 031000000000000

1-pentene 031000000000000

1,4-pentadiene 012000000000000

cyclopentene 010000000000001

normal pentene isomers 031000000000000

piperylene {1,3-pentadiene} (mixed isomers 0 0 0.5 000000000001cyclohexene 020000000000001

cis-3-hexene 020000000000001

2-hexenes 020000000000001

4-methyl-trans-2-pentene 020000000000001

trans-3-hexene 020000000000001

trans-2-hexene 020000000000001

cis-2-hexene 020000000000001

Page 4 of 15
Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Species

name NASN PA

R OLE TOL

XYL FORM

ALD2 ETH ISOP MEOH ETOH NR CH4 ETH

A IOLE

1-methylcyclopentene 020000000000001

dimethylbutene 0 3.5 0 0 0 0.5 000000000

2-methyl-2-pentene 040000000000000

3-methyl-trans-2-pentene 040000100000000

2,3-dimethyl-1-butene 050001000000000

2-ethyl-1-butene 050001000000000

2-methyl-1-pentene 050001000000000

c6 olefins (hexene isomers) 0 3 0.33 000000000000 

methylpentenes 0 3.5 0.5 000000000000 

hexadiene 001000000000001

methylcyclopentadiene 001000000000001

1-hexene 041000000000000

3-methyl-1-pentene 041000000000000

4-methyl-1-pentene 041000000000000

methylcyclohexene 030000000000001

methylhexadiene 030000000000001

3-ethyl-2-pentene 050000100000000

1-methyl cyclohexene 050000000000000

2,4,4-trimethyl-1-pentene 060001000001000c7 olefins 0 4 0.5 000000000000

ethylpentene 0 5 0.5 0 0 0 0 0 0 0 0 0 0 0 0 dimethylpentene 0 4.5 0.75 0 0 0 0 0 0 0 0 0 0 0 0 methylcyclohexadiene 011000000000001

1-heptene 051000000000000

ethylcyclopentene 051000000000000

dimethylcyclopentenes 051000000000000

3-heptene (mixed cis,trans) 030000000000001

methylhexenes 0 4 0.5 000000000000

heptenes 0 3.33 0.17 000000000000 

c8 olefins 0 4.67 0.5 00000000 0.33 000

cis-2-octene 0400000000000012,4,4-trimethyl-2-pentene (beta diisobutyl 060000100000000dimethylhexadiene 021000000000001

tetramethylcyclobutene 061000000000000

1-octene 061000000000000butoxybutene 061000000000000octatriene 002000000000001trimethylpentadiene 042000000000000

methyl heptene 0 5.33 0.67 000000000000 

trans-2-nonene 0500000000000014-nonene (mixed isomers) 050000000000001c9 olefins 0 6 0.5 000000000000

nonadiene 031000000000001ethylheptene 071000000000000trimethylhexene 0710000000000001-nonene 071000000000000c10 olefins 0 6.17 0.33 0 0 0 0 0 0 0 0 0.5 0 0 0 

Page 5 of 15
Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Species

name NASN PA

R OLE TOL

XYL FORM

ALD2 ETH ISOP MEOH ETOH NR CH4 ETH

A IOLE

3-carene 000000000000000d-limonene 000000000000000a-pinene 000000000000000b-pinene 000000000000000terpinene 000000000000000myrcene 000000000000000dimethyloctenes 060000000000001propylheptenes 0 7 0.5 000000000000methylnonenes 0 7 0.5 000000000000ethyloctenes 0 7 0.5 000000000000c12 olefins 0 7 0.5 0000000020004-phenyl-1-butene 011100000000000trans-1-phenylbutene 0111000000000001-decene 081000000000000b-phellandrene {1(7)-2-p-menthadiene} 000000000000000dl-limonene {dipentene} 000000000000000terpene 000000000000000methyldecenes 0 8 0.5 000000000000

c11 olefins 0 8 0.5 0000000000001-undecene 091000000000000

trimethylnonene 0 10 1000000000000

1-Dodecene 0 10 1000000000000

trimethyldecenes 0 10 0.5 000000000000caryophyllene 093000000000000ALKYNES - examplesacetylene 010000000001000

1-propyne 010000000000000

1-butyne (ethylacetylene) 020000000000000

2-butyne 020000000000000

1-pentyne 030000000000000

pentenyne 011000000000000hexyne 040000000000000

methylheptyne (6-methyl-2-heptyne) 060000000000000

dimethyloctyne 080000000000000ALDEYHDES - examplesbenzaldehyde 000000000007000p-tolualdehyde {4-methylbenzaldehyde} 000000000008000formaldehyde 000001000000000

acetaldehyde 000000100000000

glyoxal 010001000000000

total c2-c5 aldehydes 0 0.65 0000000000000

acrolein (2-propenal) 0 0 0.5 000000000000

propionaldehyde 010000000000000

methyl glyoxal 000001000000000

butyraldehyde 020000000000000

Page 6 of 15
Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Species

name NASN PA

R OLE TOL

XYL FORM

ALD2 ETH ISOP MEOH ETOH NR CH4 ETH

A IOLE

isobutyraldehyde 020000000000000

crotonaldehyde 001000000000000

n-pentanal (n-valeraldehyde) 030000000000000

isovaleraldehyde (3-methylbutanal) 030000000000000

2-furfural 011000000000000

2-Hexenal 021000000000000

hexanal (hexanaladehyde) 0400000000000002,4-hexadienal 001000000000001

methylhexanal 050000000000000trans, trans-2,4-heptadienal 011000000000001ethylhexaldehyde 060000000000000ALCOHOLS - examplescarvomenthol (2-p-menthanol) (2-methyl-5-( 0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 methyl alcohol 000000000100000

phenol (carbolic acid) 010000000005000

ethyl alcohol 000000000010000

ethylene glycol 020000000000000

2-Methylaminoethanol 010000000000000

n-propyl alcohol 030000000000000isopropyl alcohol 030000000000000tert-butyl alcohol 030000000001000

propylene glycol 030000000000000glycerol 0300000000000002-methoxyethanol {methyl cellosolve} {egme 030000000000000diglycolamine (2-(2-aminoethoxy)ethanol) 020000000000000n-butyl alcohol 040000000000000

isobutyl alcohol 040000000000000

sec-butyl alcohol 040000000000000

1,4-butanediol 040000000000000

butandiol 040000000000000

diethylene glycol (2,2'-oxybisethanol) 0400000000000002-ethoxyethanol {cellosolve} {egee} 040000000000000

misc. alcohols 0 4.74 0 0 0 0 0 0 0 0 0 0.1 0 0 0 

amyl alcohols 050000000000000

furfuryl alcohol 012000000000000n-pentanol 050000000000000

1-ethoxy-2-propanol 050000000000000isoamyl alcohol (3-methyl-1-butanol) 050000000000000

bis-phenol a 0 5 0 0 0 0 0 0 0 0 0 10 0 0 0 methyl carbitol {2-(2-methoxyethoxy)ethano 050000000000000diisopropylene glycol 020000000000000diethyl aminoethanol 0400000000000002-Ethyl-1,3-hexanediol 060000000002000triethylene glycol 0600000000000002-Hexyloxyethanol 060000000002000cyclohexanol 060000000000000

Page 7 of 15
Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Species

name NASN PA

R OLE TOL

XYL FORM

ALD2 ETH ISOP MEOH ETOH NR CH4 ETH

A IOLE

hexylene glycol (2-methylpentane-2,4-diol) 0600000000000001-hexanol (n-hexanol) 0600000000000004-methyl-2-pentanol (methyl isobutyl carbi 060000000000000diacetone alcohol (4-hydroxy-4-methyl-2-pe 060000000000000butyl cellosolve {2-butoxyethanol} {egbe} 060000000000000carbitol {degee} {2-(2-ethoxyethoxy)ethano 060000000000000benzyl alcohol 0001000000000002,2,4-Trimethyl-1,3-Pentanediol 0700000000010001-heptanol 070000000000000

dimethylpentanol (2,3-dimethyl-1-pentanol) 070000000000000

o-cresol (2-methyl-benzenol) 000100000000000biphenylol {2-phenylphenol} 000100000005000cresols 000100000000000octanol isomers 0 7.25 000000000 0.75 000

c8 phenols 010100000000000xylenol 0101000000000002-(2-butoxyethoxy)ethanol {butyl carbitol 080000000000000methylheptanol 0800000000000002-ethyl-1-hexanol 080000000000000dimethylbenzylalcohol 010010000000000c9 phenols 020100000000000trimethylcyclohexanol 090000000000000dimethylheptanol (2,6-dimethyl-2-heptanol) 090000000000000ethyldimethylphenol 020010000000000c10 alkylphenols 0301000000000002-N,N-Dibutylaminoethanol 080000000000000

1-decanol 0 10 0000000000000

3,7-dimethyl-1-octanol 0 10 0000000000000

a-terpineol 000000000000000c11 alkylphenols 040100000000000nonylphenol 080100000000000ETHERS - examplesethylene oxide 010000000001000

dimethyl ether 020000000000000

propylene oxide 020000000001000

dimethoxymethane (methylal) 030000000000000ethyl ether 040000000000000

methyl t-butyl ether (mtbe) 040000000001000

tetrahydrofuran 020000000000000

1,4-dioxane 040000000000000

propylene glycol methyl ether {1-methoxy-2 020000000000000

ethyl t-butyl ether 030000000001000ethyl isopropyl ether 050000000000000

t-amylmethylether (tame) 050000000001000ethylene glycol propyl ether {2-propoxyet 0500000000000004,4-Dimethyl-3-oxahexane 040000000001000

Page 8 of 15
Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Species

name NASN PA

R OLE TOL

XYL FORM

ALD2 ETH ISOP MEOH ETOH NR CH4 ETH

A IOLE

diisopropyl ether 060000000000000propylene glycol n-propyl ether 060000000000000acetal (1,1-diethoxyethane) 020000000000000ethylfuran 022000000000000

di(propylene glycol) methyl ether 050000000000000

dibutyl ether 0800000000000002-butyltetrahydrofuran 060000000000000KETONES - examplescarvone 0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 acetone 030000000000000

methyl ethyl ketone (mek) (2-butanone) 040000000000000

1-methyl-2-pyrrolidinone 0 4 0 0 0 0 0 0 0 0 0 0 0 0 0 

Methyl Isopropyl Ketone 050000000000000

methyl n-butyl ketone 060000000000000methyl isobutyl ketone 060000000000000cyclohexanone 060000000000000

dimethylcyclobutanone 060000000000000

methyl amyl ketone 0700000000000002-methyl-3-hexanone 070000000000000propylcyclohexanone 070000000002000heptanone 070000000000000methylacetophenone 010100000001000trimethylcyclopentanone 080000000000000

dihydroxynapthalenedione 020100000001000nonenone 0710000000000002,2,4,4-tetramethyl-3-pentanone 090000000000000c4 substituted cyclohexanone 0 10 0000000000000

9,10-anthraquinone 0002000000000001-aminoanthraquinone 000200000000000ORGANIC ACIDS - examplesformic acid 000000000001000

oxalic acid 000000000002000

acetic acid 010000000001000

benzoic acid 010000000006000terephthalic acid (p-benzenedicarboxylic a 010000000007000propionic acid 020000000001000

acrylic acid 001000000001000

methyacrylic acid 011000000001000

butanoic acid 030000000001000

3-Methylbutanoic acid 030000000002000isobutyric acid 030000000001000

adipic acid 0400000000020002-ethylhexanoic acid 070000000001000Phenylacetic Acid 000100000001000dimethylethylbenzoic acid 010010000000000

Page 9 of 15
Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Species

name NASN PA

R OLE TOL

XYL FORM

ALD2 ETH ISOP MEOH ETOH NR CH4 ETH

A IOLE

ESTERS - examplesmethyl formate 010000000001000

phthalic anhydride 010000000007000acetic anhydride 020000000002000methyl acetate 020000000001000

vinyl acetate 011000000001000

ethyl acetate 030000000001000

methyl acrylate 011000000001000

dimethylterephthalate 030000000007000dimethyl phthalate 030000000007000Isopropyl Formate 030000000001000

maleic anhydride 002000000000000

propyl acetate 040000000001000isopropyl acetate 040000000001000ethyl acrylate 021000000001000methyl methacrylate 021000000001000hydroxypropyl acrylate 021000000002000dimethyl succinate (dimethyl butaneoate) 040000000002000misc. esters 0 4.11 0000000001000 

c5 ester 0 4.33 000000000 0.67 000

propylene glycol monomethyl ether acetate 030000000001000n-butyl acetate 050000000001000isobutyl acetate 0500000000010002-ethoxyethyl acetate {cellosolve acetate} 050000000001000pentanedioic acid, dimethyl ester (dimethy 050000000002000n-Propyl Propionate 050000000001000n-butyl benzoate 050000000006000methyl isobutyrate 050000000000000amyl acetate 060000000001000n-butyl acrylate 041000000001000dimethyl adipate (dimethylhexanedioate) 060000000002000

isobutyl acrylate {2-propenoic acid} 041000000001000butyl methacrylate 051000000001000

dipropyl phthalate 070000000007000

2-butoxyethyl acetate (ethylene glycol but 050000000001000ethylhexanoate (ethyl n-hexanoate) 070000000001000substituted c9 ester (c12) 070000000005000substituted c7 ester (c12) 070000000005000methylethylpentanoate 070000000001000methyl amyl acetate (4-methyl-2-pentanol a 070000000001000isobutyl isobutyrate 070000000001000dipropylene glycol methyl ether acetate 0600000000010002-Ethyl-Hexyl Acrylate 061000000003000butylisopropylphthalate 080000000007000dibutyl phthalate 090000000007000diethylene glycol butyl ether acetate {2-2 090000000001000

Page 10 of 15
Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Species

name NASN PA

R OLE TOL

XYL FORM

ALD2 ETH ISOP MEOH ETOH NR CH4 ETH

A IOLE

isoamyl isobutyrate 090000000000000methyl c11 ester 0 11 0000000002000

methyl dodecanoate {methyl laurate} 0 12 0000000001000

methyl c12 ester 0 12 0000000002000

methyl myristate {methyl tetradecanoate} 0 14 0000000001000

methyl c13 ester 0 14 0000000001000

methyl c15 ester 0 16 0000000001000

AROMATIC COMPOUNDS - examplesbenzene 010000000005000

nitrobenzene 010000000005000aniline {aminobenzene} 0000 0.75 0000000000

toluene 000100000000000

methylphenanthrenes 000100000008000c2 alkylphenanthrenes 000100000003000c2 alkylanthracenes 000100000003000biphenyl {phenyl benzene} 000100000005000o-xylene 000010000000000m-xylene 000010000000000p-xylene 000010000000000m-xylene and p-xylene 000010000000000benzo[ghi]fluoranthene 0 0 0 0 1 0 0 0 0 0 0 10 0 0 0 benzo(a)anthracene 0 0 0 0 1 0 0 0 0 0 0 10 0 0 0 chrysene 0 0 0 0 1 0 0 0 0 0 0 10 0 0 0 benzo(c)phenanthrene 0 0 0 0 1 0 0 0 0 0 0 10 0 0 0 methylbenzphenanthrene 0 0 0 0 1 0 0 0 0 0 0 11 0 0 0 styrene 0 0 0.5 100000000000

methylbenzanthracenes 0 0 0 0 1 0 0 0 0 0 0 11 0 0 0 isomers of xylene 0 0.25 0 0.25 0.75 0000000000ethylbenzene 010100000000000methyl biphenyl (mixed) {phenyltoluene} 000010000005000methylchrysenes 0 0 0 0 1 0 0 0 0 0 0 11 0 0 0 indene 0 0 0.5 0100000000001,3,5-trimethylbenzene 010010000000000

1,2,4-trimethylbenzene 010010000000000

1,2,3-trimethylbenzene 010010000000000

trimethylbenzenes 010010000000000

ethyltoluenes {methylethylbenzenes} 010010000000000

o-ethyltoluene 010010000000000

m-ethyltoluene 010010000000000

p-ethyltoluene 010010000000000

c9 alkyl benzenes 0 1.38 0 0.38 0.62 0000000000

t-butylbenzene 020100000001000Isomers of propylbenzene 020100000000000

n-propylbenzene 020100000000000

cumene (isopropyl benzene) 020100000000000

methyl styrene (mixed) {vinyl toluene} 001100000000000

Page 11 of 15
Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Species

name NASN PA

R OLE TOL

XYL FORM

ALD2 ETH ISOP MEOH ETOH NR CH4 ETH

A IOLE

indan 010010000000000cumene hydroperoxide 020100000000000Butylbenzene isomers 0 2.9 0 1 0 0 0 0 0 0 0 0.1 0 0 0 

c3/c4/c5 alkylbenzenes 0 2.25 0 0.32 0.68 0000000000methylindans 020010000000000camphene 000000000000000methylindene 001010000000000divinyl benzene {vinyl styrene} 0010100000000001,3-diethylbenzene (meta) 0200100000000001,2-diethylbenzene (ortho) 0200100000000001,2,3,4-tetramethylbenzene 020010000000000ethyldimethylbenzenes 020010000000000tetramethylbenzenes 0200100000000001-methyl-2-tert-butylbenzene 0200100000010001-methyl-4-isopropylbenzene 0200100000000001-methyl-3n-propylbenzene 0200100000000001-methyl-3-isopropylbenzene 020010000000000napthalene 020010000000000dihydronaphthalene 0200100000000001-methyl naphthalene 020010000001000

diethylbenzenes 020010000000000(1-methylpropyl)benzene (sec-butyl benzene 030100000000000n-butylbenzene 030100000000000(2-methylpropyl)benzene 030100000000000ethyl styrene {ethylvinyl benzene} 011100000000000c4 alkylstyrenes 0111000000020001,3-diethylbenzene (meta) 0200100000000001,2-diethylbenzene (ortho) 020010000000000c10 aromatics 0 2.25 0 0.25 0.75 0000000000methylnaphthalenes 0 2.5 0 0 1 0 0 0 0 0 0 0.5 0 0 0 

dimethylindans 030010000000000dimethylindene 011010000000000c3 alkylstyrene 011010000000000c11 unsaturated alkylbenzenes 0110100000000001-(1,1-dimethylethyl)-3,5-dimethylbenzene 030010000001000methoxynaphthalene 030010000000000

methyldihydronaphthalene 030010000000000c11 alkylbenzenes 0 3.33 0 0.33 0.67 0000000000n-pentylbenzene 040100000000000c2 alkyl indan 030010000000000ethylindan 030010000000000diisopropyl benzene (mixed isomers) 040010000000000acenaphthylene 002010000000000

c2 alkylnaphthalene 040010000000000acenaphthene 040010000000000c12 dialkyl benzenes 040010000000000dimethyl napthalenes 040010000000000

Page 12 of 15
Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Species

name NASN PA

R OLE TOL

XYL FORM

ALD2 ETH ISOP MEOH ETOH NR CH4 ETH

A IOLE

ethylnaphthalenes 040010000000000trimethylindan 040010000000000propylnaphthalene 050010000000000trimethylnaphthalene 050010000000000fluorene 050010000000000c13 alkyl benzenes 0 5.33 0 0.33 0.67 0000000000

anthracene 022010000000000diphenyl ethane {bibenzyl} 000200000000000methylanthracenes 000110000000000fluoranthene 000020000000000pyrene 000020000000000cyclopentaphenanthrenes 000020000000000cyclopentaanthracenes 000020000000000phenylnaphthalenes 010110000000000ethyl-phenyl-phenyl-ethane 010110000000000methylfluoranthenes 010020000000000di(ethylphenyl)ethane 040200000000000cyclopenta[cd]pyrene 020020000000000HALOGENATED COMPOUNDS - examplesmethyl chloride 000000000001000

carbon tetrachloride 000000000001000dichlorodifluoromethane (f-12) 000000000001000chlorotrifluoromethane (f-13) 0000000000010001,1-dichloroethane 000000000002000

1,1,1-trichloroethane 0000000000020001,1,2-trichloroethane 000000000002000dichlorotetrafluoroethane 000000000002000ethyl chloride 000000000002000

ethylene dichloride 000000000002000

chloropentafluoroethane (f115) 000000000002000hexafluoroethane {f-116} 000000000002000methylene bromide 000000000001000ethylene dibromide 000000000002000methyl bromide 000000000001000

1,2-dichloro-1,1,2,2-tetrafluoroethane {cf 000000000002000chlorodifluoromethane (f-22) 000000000001000

trifluoromethane (f-23) 000000000001000

chlorofluorohydrocarbons 000000000002000trichlorotrifluoroethane-f113 000000000002000chloroform 000000000001000trichlorofluoromethane 000000000001000Iodomethane 000000000001000dichloromethane {methylene chloride} 000000000001000

tetrafluoromethane {carbon tetrafluoride} 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 perchloroethylene 0000000000020002,2-dichloronitroaniline 010000000005000

Page 13 of 15
Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Species

name NASN PA

R OLE TOL

XYL FORM

ALD2 ETH ISOP MEOH ETOH NR CH4 ETH

A IOLE

bromodinitroaniline {2,4-dinitro-6-bromoan 010000000005000bromodinitrobenzene 010000000005000chlorobenzene 010000000005000o-dichlorobenzene 0 1 0 0 0 0 0 0 0 0 0 5 0 0 0 1,3-dichlorobenzene {m-dichlorobenzene} 0 1 0 0 0 0 0 0 0 0 0 5 0 0 0 p-dichlorobenzene 0 1 0 0 0 0 0 0 0 0 0 5 0 0 0 dichlorobenzenes 0 1 0 0 0 0 0 0 0 0 0 5 0 0 0 trichlorobenzenes (mixed) 010000000005000tetrachlorobenzenes 010000000005000propylene dichloride 0 1.5 0 0 0 0 0 0 0 0 0 1.5 0 0 0 

1,3-Dichloropropane 0 1.5 0 0 0 0 0 0 0 0 0 1.5 0 0 0 

vinyl chloride 0000000100000001,1-dichloroethene {vinylidene chloride} 020000000000000

trichloroethylene (tce) 000000010000000Chloropropane 030000000000000

epichlorohydrin 030000000000000

Glycerol alpha-monochlorohydrin 030000000000000chloroprene (2-chloro-1,3-butadiene) 002000000000000

1-chlorobutane 040000000000000

benzyl chloride 000100000000000Benzoyl chloride 0001000000000003-(chloromethyl)-heptane 080000000000000NITROGEN containing compounds - examplesnitroethane 0 0.4 0 0 0 0 0 0 0 0 0 1.6 0 0 0 

methylamine 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 

pyridine 010000000004000phenyl isocyanate 010000000006000acetonitrile 010000000001000

hydroxyacetonitrile 010000000001000

Monomethyl Hydrazine 010000000000000

Nitropropanes 0 1.5 0 0 0 0 0 0 0 0 0 1.5 0 0 0 

dimethyl formamide 020000000001000ethylene diamine 000000010000000ethanolamine 000000000000000

ethylamine 000000000000000

dimethylamine 000000000000000

ethyleneamines 000000000000000

trimethyl amine 010000000000000

tert-butyl amine 010000000001000

isopropylamine 010000000000000

dimethyl alkyl amines 010000000000000

acrylonitrile 011000000000000

Isobutyronitrile 030000000001000

butyronitrile 030000000001000

N,N-Dimethylacetoacetamide 020000000002000dimethylacetamide 000000000000000

Page 14 of 15
Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Species

name NASN PA

R OLE TOL

XYL FORM

ALD2 ETH ISOP MEOH ETOH NR CH4 ETH

A IOLE

N-(2-Hydroxyethyl)ethylenediamine 020000000000000diethanolamine 040000000000000n,n-dimethylethanolamine 040000000000000

diethylenetriamine 020000000000000diethylamine 020000000000000

n-Butylamine 020000000000000

2-methyl-3-butenenitrile 021000000001000

methyl glutaronitrile 040000000002000morpholine (tetrahydro-1,4-oxazin) 040000000000000

caprolactam 0500000000010001,4-Diazabicyclo[2.2.2]octane 040000000000000hexamethylenediamine 040000000000000cyclohexamine 040000000000000

hexamethyleneimine 040000000000000

Diisopropanolamine 040000000000000triethanolamine 040000000000000triethylene tetramine 040000000000000triethylamine 021000000000000n-Hexylamine 040000000000000N-aminoethylpiperazine 040000000000000n-phenylaniline {diphenylamine} 0001000000050004-methylaniline 000100000000000toluene isocyanate 0001000000010002,4-toluene diisocyanate {tdi} 0001000000020002,4-Dinitrotoluene 000100000000000benzothiazole 000100000000000Tetraethylenepentamine 0600000000000004,4-methylene dianiline 010100000005000dimethylnaphthyridine 030100000000000

SULFUR containing compounds - examplescarbonyl sulfide 000000000001000

carbon disulfide 010000000000000

methyl mercaptan 010000000000000

dimethyl sulfide 020000000000000

dimethyl disulfide 020000000000000ethyl mercaptan 020000000000000

Diethyl Sulfate 040000000000000Thiophene 000000000000001

Page 15 of 15
Appendix B 

Chamber Simulations for the University of North Carolina (UNC) 

Chamber with CB05 Organized by Chemical Compound Type 
Chamber Background 

Au 07 97 

OC 10 96

07/05 1
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.05

0.10

H o u r s, L D T

NO, 

●

O3, (L)

● ● ● ● ● ● ● ●

NO, (L) NO2

, (L)

O3, (

NO, (

NO2, 

TotN

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.05

0.10

0.15

0.20

0.25

0.30

H o u r s, L D T

NO, NO2, ppm

Background August 07, 

O3, (L)

● ● ● ● ● ● ● ● ● ● ●

NO, (L) NO2

, (L)

CB05 Simulation

O3, (

NO, (

NO2, 

TotN

Background
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

● ● ●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

H o u r s, L D T

CCl

4, relative

August 07, 

● ● ● ● ● ●

● ●

● ● ●

CCl4, (L)

CCl4

● ● ● ● ● ● ● ● ● ● ●

CCl4, (R)

CCl4
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.01

0.02

0.03

0.04

H o u r s, L D T

NO, 

● ● ●

● ● ● ●

● ●

NO, (L)

●

NO2, (L)

NO, (

NO2, 

TotN

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

H o u r s, L D T

NO, NO2, ppm

Background October 10, 

O3, (L)

● ● ● ● ● ● ●

NO, (L)

●

NO2, (L)

CB05 Simulation

O3, (

NO, (

NO2, 

TotN

Background Chamber Test
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●● ● ●● ●

●

● ● ●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

H o u r s, L D T

CCl

4, relative

October 10, 

● ● ●

● ● ● ● ● ● ● ● ●

CCl4, (L)

CCl4

● ●

● ● ● ● ● ● ● ● ● ●

CCl4, (R)

CCl4
Carbon Monoxide (CO) 

JL 07 01 

JL 22 01 

AU 30 93 

ST 20 00 

OC 03 95 

07/05 6
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

O3, (L)

NO2, (L)

O

N

N

T

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

500 ppm Carbon Monoxide Jul 07, 2

● ● ● ●

O3, (L)

NO, (L)

NO2, (L)

CB05 Simulation

O

N

N

T

Delta CO (filtered); NOx Matched
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

H o u r s, L D T

CCl

4, relative

Jul 07, 2

● ● ● ● ● ●

● ●

● ● ● ●

CCl4, (L)

C

● ● ● ●

●

●

●

●

●

●

●

CCl4, (R)

C
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

●

NO, (L) NO2

, (L)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

400 ppm Carbon Monoxide Jul 22, 2

●

O3, (

NO, (L)

NO2, (L)

CB05 Simulation

Matched Carbon Monoxide; Delta NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

H o u r s, L D T

CCl

4, relative

Jul 22, 2

●

● ● ● ●

●

●

●

●

●

● ●

●

CCl4, (L)

● ● ● ● ●

●

●

●

● ●

● ●

CCl4, (R)
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

H o u r s, L D T

NO, 

● ● ●

NO, (L) NO2

, (L)

N

N

To

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

1.5

H o u r s, L D T

NO, NO2, ppm

100 ppm CO August 30, 

O3, (L)

●

NO, (L) NO2

, (L)

CB05 Simulation

O

N

N

To

Delta CO
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

●

●

●

●
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

●

O3, (L)

●

NO, (L) NO2

, (L)

O

N

N

T

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

500 ppm Carbon Monoxide Sep 20, 

O3, (L)

● ● ● ●

NO, (L) NO2

, (L)

CB05 Simulation

O

N

N

T

500 vs 250 ppm CO; matched 0.33 NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●●●●

●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

H o u r s, L D T

CCl

4, relative

Sep 20, 

● ● ●

● ● ● ● ●

●

●

●

●

●

CCl4, (L)

C

● ● ● ● ● ● ●

●

● ●

●

●

CCl4, (R)

C
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

NO, (L)

NO2, (L)

O

N

N

T

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

250 ppm CO Non-filtered October 03, 

O3, (L)

NO, (L) NO2

, (L)

CB05 Simulation

O

N

N

T

Matched CO and NOx; BLUE CO filtered with 13x Molesieve
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

● ●●●●●● ●

●●● ●● ● ●●●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

H o u r s, L D T

CCl

4, relative

October 03, 

● ● ● ● ● ● ● ● ● ●

CCl4, (L)

C

● ● ● ● ● ● ● ● ●

CCl4, (R)

C
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

●

O3, (L)

●

NO, (L) NO2

, (L)

O

N

N

T

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

500 ppm Carbon Monoxide Sep 20, 

O3, (L)

● ● ● ●

NO, (L) NO2

, (L)

CB05 Simulation

O

N

N

T

500 vs 250 ppm CO; matched 0.33 NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●●●●

●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

H o u r s, L D T

CCl

4, relative

Sep 20, 

● ● ●

● ● ● ● ●

●

●

●

●

●

CCl4, (L)

C

● ● ● ● ● ● ●

●

● ●

●

●

CCl4, (R)

C
Formaldehyde (FORM) 

JL 08 86 

JL 15 88 

ST 23 97 

ST 30 97 

07/05 19
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

NO, (L)

NO2, (L)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

1.03 ppm Formaldehyde July 8, 1

O3, (L)

●

NO, (L) NO2

, (L)

1.03 PPM FORMALDEHYDE (HCHO)-BLUE

Delta HCHO at 0.17 NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

VO

●

●

●

●

●

●

●

● ● ●

FORM

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

VOC, ppmC

July 15, 1

● ●

● ●

●

●

●

●

●

● ●

● ● ●●

Formaldehyde-PKD

FORM
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

● ● ● ● ● ●

NO, (L) NO2

, (L)

NO, (L)

NO2, (L) TotNO3, 

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

0.43 ppmC Formaldehyde July 15, 19

O3, (L)

NO, (L)

NO2, (L)

CB05 Simulation

O3, (L)

NO, (L)

NO2, (L) TotNO3, 

Delta HCHO at 0.3 ppm NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

●●

●

●

●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

CCl4, relative

July 15, 19

CCl4, (L) CCl4, (R
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

VO

✕

✕

✕ ✕

✕ ✕

✕ ✕ ✕

FOR

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

VOC, ppmC

1.0 ppm Formaldehyde September 23

✕

✕

✕

✕

✕

✕

✕

✕

✕

✕

✕

✕ ✕

✕

✕

HCHO

1 PPM FORMALDEHYDE (HCHO)-BLUE

FOR
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

H o u r s, L D T

NO, 

O3, (L)

NO2, (L)

O3, (

NO, 

NO2, 

TotN

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

H o u r s, L D T

NO, NO2, ppm

1.0 ppm Formaldehyde September 23

O3, (L)

● ● ● ● ●

NO, (L)

NO2, (L)

1 PPM FORMALDEHYDE (HCHO)-BLUE

O3, (

NO, 

NO2, 

TotN

Delta Formaldehyde
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●● ● ●

●●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

H o u r s, L D T

CCl

4, relative

September 23

● ●

● ● ● ●

●

●

●

● ● ●

CCl4, (L)

● ● CCl4

● ● ● ● ● ● ● ● ● ●

CCl4, (R)

CCl4
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

● ●

NO, (L) NO2

, (L)

NO, (L) NO2, (L) TotNO3, (L)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

250 ppm CO September 30

O3, (L)

NO, (L) NO2

, (L)

CB05 Morpho Model Simulaton

O3, (L)

NO, (L)

NO2, (L) TotNO3, (L)

Characterization: Formaldehyde vs CO; matched NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●● ●● ●

● ●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

H o u r s, L D T

CCl

4, relative

September 30

● ●

CCl4, (L)

●

●

CCl4, (R)
Methane (CH4) 

JL 21 91 

AU 01 97 

AU10 92 

ST 07 90 

ST 19 96 

ST 20 93 

07/05 30
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

H o u r s, L D T

VO

▲

▲ ▲

▲

▲

▲

▲

▲

▲ ▲

▲

▲ ▲

▲

▲

▲

▲

▲

FORM

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

H o u r s, L D T

VOC, ppmC

July 21, 1

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲▲

▲▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲▲

▲

▲

▲

▲

▲

▲

▲

▲

▲▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲▲

▲

▲

▲

▲

▲

▲

▲

▲

▲▲

▲

▲

▲

▲

▲

▲

CO, (R)

▲

▲ ▲ ▲ ▲ ▲ ▲

▲▲

▲ ▲

▲▲ ▲ ▲

▲▲ ▲▲

Formaldehyde, (R)

FORM
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

NO, (L)

NO2, (L)

NO, (

NO2, 

TotN

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

250 ppmC Methane July 21, 1

O3, (L)

NO, (L)

NO2, (L)

CB05 Simulation

O3, (

NO, (

NO2, 

TotN

Run C1-- Delta Methane
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

●●

●●

●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

CCl4, relative

July 21, 1
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

● ●

NO, (L)

NO2, (L)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

250 ppm Methane August 01, 

● ● ● ●

O3, (L)

NO, (L)

NO2, (L)

CB05 Simulation

250 vs 500 ppm Methane; 0.35 NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

H o u r s, L D T

NO, 

● ● ●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

0.60

H o u r s, L D T

NO, NO2, ppm

250 ppm Methane August 10, 

●

O3, (L)

NO, (L)

NO2, (L)

CB05 Simulation

CRC Run C1-- Delta Methane
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

● ●●● ●●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

H o u r s, L D T

CCl

4, relative

August 10, 
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.05

0.10

H o u r s, L D T

NO, 

O3, (L)

O3, 

NO, 

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.05

0.10

0.15

0.20

0.25

0.30

H o u r s, L D T

NO, NO2, ppm

394 ppm Methane September 7

O3, (L)

NO, (L)

NO2, (L)

CB05 Simulation

O3, 

NO, 

NO2

TotN

Matched Methane
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

● ●● ● ●●

● ●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

H o u r s, L D T

CCl

4, relative

September 7

CCl4CCl4
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

H o u r s, L D T

NO, 

O3, (L

●

NO2, (L)

O

N

N

T

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

0.60

H o u r s, L D T

NO, NO2, ppm

600 ppmC Methane September 19

O3, (L

NO, (L)

NO2, (L)

CB05 Simulation

O

N

N

T

Delta Methane
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

● ● ● ●●

●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

H o u r s, L D T

CCl

4, relative

September 19

● ●

● ● ● ●

● ● ● ● ● ● ●

CCl4, (L)

C

●

● ● ● ● ● ● ● ● ● ● ● 

CCl4, (R)

C
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

O3, (L)

NO, (L)

NO2, (L)

O3, (L

NO, (L

NO2, 

TotNO

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

500 ppm Methane September 20

O3, (L)

NO, (L)

NO2, (L)

CB05 Simulation

O3, (L

NO, (L

NO2, 

TotNO

500 vs 250 Methane 
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

●

●

●

●
Acetaldehyde (ALD2) 

JL 09 97 

JL 18 97 

AU 17 78 

07/05 44
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

1.0

2.0

H o u r s, L D T

VO

●

●

●

●

●

● ● ● ● ● ● ● ● ● ● ●

HCHO, (L)

F

A

C

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.5

1.0

1.5

2.0

2.5

3.0

H o u r s, L D T

VOC, ppmC

July 09, 1

■

■ ■ ■

■

■

■

■

■

■

■

Acetaldehyde, (L)

■ ■ ■ ■

■ ■ ■ ■ ■ ■ ■ ■

HCHO, 

F

A

C
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

●

● ● ● ● ●

NO, (L)

NO2, (L)

PAN, 

N

N

P

T

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

2.23 ppmC Acetaldehyde July 09, 1

O3, (L)

● ● ●

NO, (L) NO2

, (L)

1.12 PPM ACETALDEHYDE-BLUE

O

N

N

P

T

Acetaldehyde vs Isobutyraldehyde
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

H o u r s, L D T

CCl4, relative

July 09, 1

C
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

VO

■ ■ ■

■ ■ ■

■

■ ■

■ ■

Butyraldehyde

▼ ▼

▼

▼

▼

▼

▼

▼

▼

▼

✕ ✕ ✕ ✕ ✕

✕

✕

✕

✕ ✕ ✕

HCHO

F

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

VOC, ppmC

0.4 ppmV Butyraldehyde + 0.4 ppmV Acetaldehyde July 18, 1

▲ ▲ ▲

▲

▲

▲

▲

▲ ▲ ▲

▲ ▲

Propionaldehyde

✕ ✕ ✕

✕

✕

✕ ✕

✕

✕

✕ ✕

HCHO

F
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.5

1.0

H o u r s, L D T

VO

●

●

●

●

● ●

▲

▲ ▲

▲ ▲

▲

▲

▲

▲

▲ ▲

A

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.5

1.0

1.5

2.0

2.5

3.0

H o u r s, L D T

VOC, ppmC

0.4 ppmV Butyraldehyde + 0.4 ppmV Acetaldehyde July 18, 1

■

■ ■

■

■

■

■

■

■

■

■ ■

Butyraldehyde

▼ ▼ ▼

▼ ▼

▼ ▼

▼

▼ ▼ ▼ ▼

Acetaldehyde

A

A

● ● ● ● ● ● ● ●

●

●

●

CCl4

C
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

● ● ● ● ● ●

NO, (L) NO2

, (L)

PAN, (L)

N

N

P

T

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

0.4 ppmV Butyraldehyde + 0.4 ppmV Acetaldehyde July 18, 1

O3, (L)

● ● ●

NO, (L) NO2

, (L)

ALDX Simulation O

N

N

P

T

Aldehyde Mix and NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

● ● ● ● ● ●

NO, (L) NO2

, (L)

PAN, (L)

N

N

P

T

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

0.4 ppmV Butyraldehyde + 0.4 ppmV Acetaldehyde July 18, 1

O3, (L)

● ● ●

NO, (L) NO2

, (L)

ALDX Simulation O

N

N

P

T

Aldehyde Mix and NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

H o u r s, L D T

VO

■

■

■

■

■

ALD2

FOR

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

1.5

H o u r s, L D T

VOC, ppmC

August 17, 1

■

■

■

Acetaldehyde, (L) ALD2

▲ ▲

▲ ▲

▲ ▲ ▲

▲

▲ ▲

▲

▲

▲

▲

CO, (R)

CO, (

FOR
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

H o u r s, L D T

NO, 

O3, (L)

O3, (

NO, (

NO2, 

TotN

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

H o u r s, L D T

NO, NO2, ppm

4.00 ppmC Acetaldehyde August 17, 1

O3, (L)

NO, (L) NO2

, (L)

CB05 Simulation

O3, (

NO, (

NO2, 

TotN

Delta HC at 0.70 ppm NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

H o u r s, L D T

CCl

4, relative

August 17, 1

CCl4CCl4
Higher Aldehydes (ALDX) 

JL 03 97 

AU 12 97 

ST 04 97 

OC 04 96 

07/05 55
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.5

1.0

H o u r s, L D T

Al

▲

▲

▲

▲

▲

▼ ▼

▼

▼

▼

▼

▼

▼ ▼ ▼ ▼

Acetaldehyde

✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕

HCHO

ALD2

FOR

ALDX

●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.5

1.0

1.5

2.0

2.5

3.0

H o u r s, L D T

ALD2, ppmC

July 03, 1

▼

▼ ▼ ▼

▼

▼

▼

▼

▼

▼

▼

Acetaldehyde, (L)

ALD2

✕

✕

✕

✕

✕

✕

✕ ✕

✕

✕

✕

✕ ✕ ✕ ✕ ✕

✕

HCHO, (R)

FOR

CCl4
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

H o u r s, L D T

NO, 

● ● ● ●

NO, (L) NO2

, (L)

NO, (

NO2, 

TotN

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

H o u r s, L D T

NO, NO2, ppm

1.888 ppmC Acetaldehyde July 03, 1

O3, (L)

● ● ● ●

NO, (L) NO2

, (L)

CB05 Simulation O3, (

NO, (

NO2, 

TotN

Acetaldehyde vs Propionaldehyde
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

VO

■ ■ ■

■

■

■

■

■

■

■

■ ■

Acetaldehyde

▲ ▲ ▲ ▲

▲

▲

▲

▲

▲

▲ ▲

HCHO, (R)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

VOC, ppmC

August 12, 

■ ■ ■ ■

■

■

■

■

■

■ ■

Acetaldeh

▲ ▲

▲

▲

▲

▲

▲

▲

▲

▲

▲ 

HCHO, (
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

H o u r s, L D T

NO, 

NO, (L) NO2

, (L)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

H o u r s, L D T

NO, NO2, ppm

1.0 ppm 2-hexanone + 1.0 ppm 2-butanone August 12, 

O3, (L)

NO, (L)

NO2, (L)

CB05 Simulation

Aldehydes Mix vs Ketones Mix
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

H o u r s, L D T

CCl

4, relative

August 12, 

●

CCl4, (L)
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

● ●

NO, (L) NO2

, (L)

PAN, (L)

NO, (

NO2, 

PAN, 

TotN

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

0.5 ppmV Isobutyraldehyde + 0.5 ppmV propionaldehyde September 04

O3, (L)

● ● ● ● ● ●

NO, (L) NO2

, (L)

ALDX Simulation

O3, (

NO, (

NO2, 

PAN, 

TotN

Aldehyde Mix run
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

● ● ●●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

H o u r s, L D T

CCl

4, relative

September 04

CCl4
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.5

1.0

H o u r s, L D T

VO

▼

▼

▼ ▼ 

✕✕ ✕✕ ✕✕ ✕✕ ✕✕ ✕✕ ✕✕ ✕✕ ✕

Formaldehyde

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.5

1.0

1.5

2.0

2.5

3.0

H o u r s, L D T

VOC, ppmC

Oct 04, 

▲ ▲ ▲

▲

▲

▲

▲

▲

▲

▲ ▲ 

Priopionaldehyde

▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ 

Acetaldehyde

✕✕ ✕✕ ✕✕ ✕✕ ✕✕ ✕✕ ✕✕ ✕✕ 

Formaldehyd

Pr

▲▲

▲▲ ▲

▲ ▲▲ ▲▲ ▲▲ ▲▲ ▲▲ 

Formaldehyd
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

O3, (L)

● ● 

NO, (L) NO2

, (L)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

1.0 ppmC Acetaldehyde + 1.5 ppmC PropionaldehydeOct 04, 

O3, (L)

● ● ● ● ● ● 

NO, (L) NO2

, (L)

CB05 Simulation

1 ppm Acetaldehyde vs 0.5 ppm Acetaldehyde and 0.5 ppm Pr
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

●●

●●

●

●●

●

●●
Ethene (ETH) 

AU 16 88 

Au 24 97 

07/05 67
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

HC

■

■

■

■ ■

■

■

■ ■ ■ ■ ■

FORM

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.5

1.0

1.5

2.0

H o u r s, L D T

ETHENE FORM, ppmC

August 16, 1

▼ ▼ ▼ ▼

▼

▼

▼

▼

▼

▼

▼

Ethene

✕ ✕ ✕ ✕ ✕ ✕

✕✕

✕

✕

✕

✕ ✕ ✕ ✕ ✕ ✕ ✕

Formaldehyde-PKD

ETH

FORM

H2

●● ●● ●● ●● ●● ●● ●● ●●

CCl4

CCl4
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

● ●

NO, (L)

NO2, (L)

O3, (L)

NO, (L)

NO2, (L

TotNO3

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

1.94 ppmC Ethene August 16, 1

O3, (L)

● ● ●

NO, (L)

NO2, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L

TotNO3

HC Reactivity at 0.39 NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●●

●

●

●

●

●
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

1.0

2.0

H o u r s, L D T

VO

■

■

■

■

ETH, (

▲ ▲

▲

▲

HCHO, (R)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

1.0

2.0

3.0

4.0

5.0

H o u r s, L D T

VOC, ppmC

August 24, 

■ ■ ■

■

■

■

■

■

■ ■

Ethene, (L)

ETH, (

▲ ▲ ▲

▲

▲

▲

HCHO, 

FORM
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

H o u r s, L D T

NO, 

● ● ● ● ● ● ● ●

NO, (L) NO2

, (L)

NO, (L

NO2, 

TotNO

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

H o u r s, L D T

NO, NO2, ppm

3.68 ppmC Ethene August 24, 

● ●

O3, (L)

● ● ● ●

NO, (L) NO2

, (L)

CB05 Simulation

O3, (L

NO, (L

NO2, 

TotNO

Matched 4 ppmC Ethene
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

●● ●●●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

H o u r s, L D T

CCl

4, relative

August 24, 
Terminal Olefins (OLE) 

JN 23 92 

ST 19 95 

07/05 74
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.5

H o u r s, L D T

VO

■

■

■

■

■

■

■ ■ ■

OLE, 

▲

▲

▲▲

▲▲

▲

▲▲

▲

▲

▲▲

▲

▲

▲

▲

▲

▲

▲

▲ ▲

▲

▲

▲

▲

▲

▲ ▲ ▲ ▲ ▲ ▲

▲ ▲

FOR

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.5

1.0

1.5

2.0

H o u r s, L D T

VOC, ppmC

June 23, 

■ ■ ■ ■

■

■

■

■

■

■ ■ ■

Propene, (L)

OLE, 

▲

▲

▲

▲

▲

▲▲

▲

▲

▲

▲

▲▲▲

▲▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲▲

▲

▲

▲

▲

▲

▲

▲

▲▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲▲

▲

▲

▲

▲▲

●

CO, (R)

▲

▲

▲

▲

▲ ▲

▲

▲

▲

▲ ▲

▲ ▲

HCHO, (R)

FOR
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

H o u r s, L D T

NO, 

● ● ●

●

PAN, (L)

NO, (

NO2, 

PAN, 

TotN

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

H o u r s, L D T

NO, NO2, ppm

1 ppmC Propylene June 23, 

● ●

O3, (L)

NO, (L)

NO2, (L)

CB05 Simulation

O3, (

NO, (

NO2, 

PAN, 

TotN

Matched Propylene; Matched NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

●●

●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

H o u r s, L D T

CCl4, relative

June 23, 

CCl4CCl4
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

H o u r s, L D T

NO, 

● ● ● ● ●

PAN, (L)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

H o u r s, L D T

NO, NO2, ppm

4.00 ppmC Ethene September 19

O3, (L)

● ● ● ● ● ● ● ● ●

NO, (L) NO2

, (L)

CB05 Simulation

Propene vs Ethene run; Matched NOx 
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

1.0

2.0

3.0

H o u r s, L D T

VO

● ● ●

●

●

●

●

● ● ● ● ● ● ● ● ●

▼

▼

▼ ▼ ▼ ▼ ▼

▼

▼

▼

▼

▼ ▼

▼

▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼

ACETALDEHYDE

✕ ✕

✕ ✕

✕

✕ ✕

Formaldehy

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

H o u r s, L D T

VOC, ppmC

4.00 ppmC Ethene September 19

■ ■ ■ ■ ■ ■ ■

■

■

■

■

■

■

■

■

■

■

■

■

■ ■

■

ETHENE

✕ ✕ ✕ ✕ ✕

✕✕

✕

✕✕

Formalde

CB05 Simulation
Olefin Mixtures (OLE and IOLE) 

AU 13 97 

ST 13 02 

ST 14 96 

OC 16 96 

07/05 80
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

1.0

H o u r s, L D T

VO

●

●

●

● ● ● ● ●

✕

✕

✕

✕

✕

HCHO

OLE

ALD2

FORM

CO

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

1.0

2.0

3.0

4.0

H o u r s, L D T

VOC, ppmC

0.2 ppm Propene, Isobutene, 1-Pentene, 1-HexeneAugust 13, 

■ ■ ■ ■

■

■

■

■ ■ ■ ■ ■

Propene ▲ ▲ ▲ ▲

▲

▲

▲ ▲ ▲ ▲ ▲ ▲

Isobutene

▼

▼ ▼ ▼

▼

▼

▼

▼ ▼ ▼ ▼ ▼

1-Pentene

◆ ◆ ◆

◆

◆

◆

◆

◆ ◆ ◆ ◆ ◆

1-Hexene

✕ ✕ ✕ ✕

✕

✕

✕

✕

✕ ✕

✕

HCHO

0.2 ppm Propene, Isobutene, 1-Pentene, 1-Hexene

PAR

OLE

ALD2

ALDX FORM

CO
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

NO, (L) NO2

, (L)

PAN, (L)

NO, (L) NO2, (L)

PAN, (L)

TotNO3, (L

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

0.2 ppm Propene, Isobutene, 1-Pentene, 1-HexeneAugust 13, 

O3, (L)

●

NO, (L) NO2

, (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L) PAN, (L)

TotNO3, (L

C3alkene vs. C3, C4, C5, C6alkenes
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

● ●

●●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

H o u r s, L D T

CCl

4, relative

August 13, 

CCl4, (L) CCl4, (R)
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

H o u r s, L D T

NO, 

NO, (L)

NO2, (L)

N

N

P

T

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

H o u r s, L D T

NO, NO2, ppm

3.0 ppmC SynUrban Terminal Alkenes September 13

O3, (L)

NO, (L)

NO2, (L)

CB05 Simulation

O

N

N

P

T

Delta SynUrban Mix Terminal Alkenes
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●●

●

●

●
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

H o u r s, L D T

NO, 

●

● ●

NO

NO

PA

To

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

0.60

H o u r s, L D T

NO, NO2, ppm

2.0 ppmC All Butenes (equal molar) September 14

O3, (L)

● ● ● ● ● ● ● ● ● ●

NO, (L)

NO2, (L)

CB05 Simulation

O3

NO

NO

PA

To

Delta Equal Molar Butenes Mix
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

●

●

●
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

H o u r s, L D T

NO, 

● ● ● ●

● ● ● ● ● 

NO, (L) NO2

, (L)

PAN, (L)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

H o u r s, L D T

NO, NO2, ppm

0.98 ppmC Propene + 1.32 ppmC 1-Butene + 1.66 ppmC 1-Pentene October 16, 

● ● ●

O3, (L)

● ● ● ● ●

NO, (L) NO2

, (L)

CB05 Simulation

Propene vs Propene, 1-Butene, 1-Pentene
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●● ● ●● ●●●

●●● ●● ● ●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

1.0

2.0

3.0

4.0

5.0

H o u r s, L D T

CCl

4, relative

October 16, 

● ● ● ● ● ● ● ● ● ● ● ● 

CCl4, (L)

● ● ● ● ● ● ● ● ● ● ● 

CCl4, (R)
Alkanes (PAR) 

MY 22 92 

MY 23 92 

AU 16 96 

AU 19 83 

OC 11 01 

07/05 90
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

H o u r s, L D T

VO

FORM

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 5

 10

 15

 20

 25

 30

H o u r s, L D T

VOC, ppmC

May 22, 

■ ■ ■ ■ ■ ■

■ ■ ■

■

N-Butane, (L)

PAR, (

CO, (R

FORM
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

● ●

NO, (L) NO2

, (L)

O3, (L)

NO, (L)

NO2, (

PAN, (

TotNO

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

24 ppmC Butane May 22, 

O3, (L)

● ●

NO, (L) NO2

, (L)

CB05 Simulation

O3, (L)

NO, (L)

NO2, (

PAN, (

TotNO

Delta Butane Run 
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

H o u r s, L D T

CCl4, relative

May 22, 
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

H o u r s, L D T

VO

▲ ▲ ▲

▲

▲

▲

▲

▲

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 5

 10

 15

 20

 25

H o u r s, L D T

VOC, ppmC

May 23, 

■

N-Butane, (L)

▲ ▲ ▲

▲

▲

▲

▲

▲

▲

▲

▲

Acetald
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

19.7 ppmC Butane May 23, 

NO, (L) NO2

, (L)

CB05 Simulation

Delta Butane Run 
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

●●

●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

H o u r s, L D T

CCl4, relative

May 23, 
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

H o u r s, L D T

VO

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

Ethane, (L)

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

Butane, (L)

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

Hexane, (L)

■ ■ ■ ■ ■ ■

■ ■ ■ ■ ■

E

F

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 5

 10

 15

 20

H o u r s, L D T

VOC, ppmC

August 16, 

■

■ ■ ■ ■ ■ ■ ■ ■ ■ ■

Ethane, (L)

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

Butane, (L)

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

Hexane, (L)

■ ■ ■ ■ ■ ■ ■ ■ ■ ■

■ ■

Octane, (L)

P

E

C

F
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

H o u r s, L D T

NO, 

●

NO2, (L)

PAN, 

N

N

P

T

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

H o u r s, L D T

NO, NO2, ppm

1.0 ppmV each of C2, C4, C6, C8 n-Alkane Mix August 16, 

O3, (L)

●

NO, (L)

NO2, (L)

CB05 Simulation

O

N

N

P

T

40 ppmC Alkane Mix vs 20 ppmC Alkane Mix
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

H o u r s, L D T

NO, 

PAN, (L)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

H o u r s, L D T

NO, NO2, ppm

4.0 ppmC 2,2,4-Trimethylpentane August 19, 1

O3

NO, (L)

NO2, (L)

CB05 Simulation

HC Reactivity at 0.37 NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

H o u r s, L D T

CCl

4, relative

August 19, 1

● ●

●

CCl4, (L)

● ● ● ●

CCl4, (R)
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

● ● ●

O3, (L)

NO, (L)

NO2, (L)

O3, (

NO, 

NO2

TotN

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

40 ppmC n-Butane Oct 11, 2

● ●

O3, (L)

NO, (L)

NO2, (L)

CB05 Simulation

O3, (

NO, 

NO2

TotN

Characterization Experiment: CH4 vs Butane
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

CCl4, relative

Oct 11, 2

CCl4CCl4
Aromatics (TOL and XYL) 

AU 01 83 

AU 03 95 

AU 17 88 

AU 22 97 

AU 30 95 

ST 13 93 

ST 14 81 

ST 24 96

07/05 104
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

1.0

2.0

H o u r s, L D T

VO

■

■

■

■

▲

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

1.0

2.0

3.0

4.0

5.0

H o u r s, L D T

VOC, ppmC

August 1, 

■ ■ ■

■

■

■

■

■ ■ ■

o-Xylene, (L)

▲

▲

▲

▲

▲

●

CO, (R)
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

●

● ●

NO, (L)

NO2, (L)

PAN, (L)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

2.6 ppmC o-Xylene August 1, 

O3, (L)

● ● ●

NO, (L)

NO2, (L)

CB05 Simulation

HC Reactivity at 0.38 pm NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

H o u r s, L D T

CCl

4, relative

August 1, 

● ● ● ● ●

● ● ● ● ● ●

CCl4, (L)

● ● ● ● ● ●

● ● ● ● ●

CCl4, (R)
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

H o u r s, L D T

VO

■

■

■

■

XYL, (L)

▲ ▲

▲ ▲

▲ ▲

▲ ▲

▲

▲

▲ ▲

▲ ▲▲

FORM, (R)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

1.5

H o u r s, L D T

VOC, ppmC

August 03, 

■

■

■

■

■

■

■ ■

1,3,5-trimethylbenzene, (L)

XYL, (L)

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲ ▲

▲

▲

▲

▲

▲

FORMALDEHYDE, (R)

FORM, (R)
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

H o u r s, L D T

NO, 

PAN, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

H o u r s, L D T

NO, NO2, ppm

1 ppm 1,3,5-Trimethylbenzene August 03, 

● ●

O3, (L)

NO, (L)

NO2, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)

Aromatics Experiments;
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

● ●●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

H o u r s, L D T

CCl

4, relative

August 03, 

● ● ● ● ● ● ● ● ●

CCL4, (L)

CCl4, (L) ● ● ● ● ● ● ● ●

CCL4, (R)

CCl4, (R)
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

1.0

2.0

H o u r s, L D T

VO

■

■

■

■ ■

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

Formaldehyde-PKD, (L)

TOL, 

FOR

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.5

1.0

1.5

2.0

H o u r s, L D T

VOC, ppmC

August 17, 

■

■

■

■

■

■ ■

■

■ ■

m-Xylene, (L)

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

Formaldehyde-PKD, (L)

XYL, 

FOR
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

H o u r s, L D T

NO, 

NO, (L)

NO2, (L)

PAN, (L)

NO, (

NO2, 

PAN, 

TotN

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

H o u r s, L D T

NO, NO2, ppm

1.715 ppmC m-Xylene August 17, 

O3, (L)

NO, (L)

NO2, (L)

CB05 Simulation O3, (

NO, (

NO2, 

PAN, 

TotN

HC Reactivity at 0.36 ppm NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

H o u r s, L D T

CCl

4, relative

August 17, 

●●● ●●● ●●● ●

●● ●●● ● ● ●● ●● ●● ●● ●●

CCl4, (L)

● ● ● ● ● ● ●● ●● ●● ●●

CCl4, (R)
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

H o u r s, L D T

VO

TOL, (L)

▲ ▲ ▲ ▲ ISOP, (L

▲

▲

▲

▲

▲ ▲ ▲

HCHO, (R)

FORM, (

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

 11

 12

 13

 14

 15

H o u r s, L D T

VOC, ppmC

August 22, 

TOL, (L)

▲ ▲ ▲

▲

▲

▲

▲

▲

▲ ▲ ▲

HCHO, (R)

FORM, (
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

● ●

●

PAN, (L)

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, 

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

2.22 ppmC Toluene, 2.84 ppmC p-xylene, 3.08 ppmC 1,3,5-trimethbeAugust 22, 

O3, (L)

NO, (L)

NO2, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, 

Toluene vs 1,3,5-trimethylbenzene, p-xylene and Toluene
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●●

●● ● ●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

H o u r s, L D T

CCl

4, relative

August 22, 

CCl4, (L) CCl4, (R
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.9

1.9

2.8

3.8

H o u r s, L D T

VO

■

■

■

■

■ ■

■ 

▲

▲

▲

▲

▲

▲

▲

▲

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.9

1.9

2.8

3.8

4.7

5.7

6.6

7.6

8.5

H o u r s, L D T

VOC, ppmC

August 30, 

■

■ ■

■

■

■

■

■

■

■ ■ 

TOLUENE, (L)

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

ACETALDEHYDE, (L)

▲ 

▲

▲

▲

▲ ▲

▲ ▲ ▲ ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲ 

Formaldehyde, (R)
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

● ● ● ●

PAN, (L)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

7 ppmC Toluene August 30, 

● ● ● ● ● ●

O3, (L) NO, (L)

NO2, (L)

CB05 Simulation

Toluene vs m-Xylene;
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

● ●

● ●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

H o u r s, L D T

CCl

4, relative

August 30, 

● ● ● ● ● ● ● ● ● ● ● ● 

CCl4, (L)

● ● ● ● ● ● ● ● ● ● ● ● 

CCl4, (R)
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

H o u r s, L D T

VO

■

■

■

■

■ ■ ■ ■

■ ■ ■ ■ ■ ■ ■ ■

■ ■

■ ■ ■ ■ ■ ■ ■ ■ ■ ■

FORMALDEHYDE, (L)

XYL, 

▲

▲▲

▲

▲

FOR

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.5

1.0

1.5

2.0

H o u r s, L D T

VOC, ppmC

September 13

■

■ ■ ■

■

■

■

■

■

■

■

TOLUENE, (L)

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

FORMALDEH

TOL, 

▲

▲

▲▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲▲

▲

▲▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲▲

▲

▲

▲

▲

▲

▲

▲

▲▲

▲

▲▲

▲

▲

▲

▲

▲

▲▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

▲

CO, (R)

CO, (

FOR
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

H o u r s, L D T

NO, 

●

● ●

NO, (

NO2, 

PAN, 

TotN

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

H o u r s, L D T

NO, NO2, ppm

1.909 ppmC Toluene September 13

● ● ●

O3, (L)

NO, (L)

NO2, (L)

CB05 Simulation

O3, (

NO, (

NO2, 

PAN, 

TotN

Toluene vs m-Xylene
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

● ● ●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

H o u r s, L D T

CCl

4, relative

September 13

● ● ● ● ● ● ● ● ● ● ●

CCl4, (L)

CCl4

● ● ● ● ● ● ● ● ● ●

CCl4, (R)

CCl4
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

VO

■

■

■

■

■ ■ ■ ■ ■

■

■ ■ ■ ■

Propene, (L)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲▲

HCHO, (R)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

VOC, ppmC

September 14, 

■ ■ ■ ■

■

■

■

■

Toluene, (L)

■ ■ ■ ■ ■

■

■ ■ ■ ■

Propene, (L)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲

HCHO, (R)
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

H o u r s, L D T

NO, 

NO, (L)

●

NO2, (L)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

H o u r s, L D T

NO, NO2, ppm

1.65 ppmC UNCMIX80, 0.52 ppmC TolueneSeptember 14, 

O3, 

NO, (L) NO2

, (L)

CB05 Simulation

HC Reactivity at 0.25 ppm NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

H o u r s, L D T

CCl

4, relative

September 14, 

● ● ● ● ●

CCl4, (L) ● ● ● ● ●

CCl4, (R)
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

H o u r s, L D T

VO

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

■

■

■ ■ ■ ■ ■

T

IS

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

 11

 12

 13

 14

 15

H o u r s, L D T

VOC, ppmC

September 24

■ ■

■

■

■

■

■

■

■

■

Toluene, (L)

T

●

●▲

▲▲

▲▲▲▲▲▲▲▲▲▲▲

▲▲▲▲

▲▲

▲▲

CO, (R)

▲

▲ ▲

▲ ▲

▲ ▲

▲

▲

▲

▲

▲ ▲ ▲

HCHO, (R)

F
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

●

● ● ● ● ● ● ● ● ●

PAN, (L)

O

N

N

P

T

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

13.37 ppmC Toluene September 24

O3, (L)

● ● ● ● ●

NO, (L)

NO2, (L)

CB05 Simulation

O

N

N

P

T

Toluene vs Isoprene
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

● ● ●

●●●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

H o u r s, L D T

CCl

4, relative

September 24

● ● ● ● ● ● ● ● ● ● ●

CCl4, (L)

C

● ● ● ● ● ● ● ● ● ●

CCl4, (R)

C
Isoprene (ISOP)

JN 26 97 

AU 06 96 

ST 11 99 

ST 24 96

07/05 129
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

1.0

2.0

3.0

H o u r s, L D T

VO

●

●

● ● ● ● ● ●

◆ ◆ ◆ ◆ ◆ ◆

◆ ◆ ◆ ◆ ◆ ◆

HCHO, (L)

ISOP, (L)

FORM, (L)

● ● ● ●

● ● ● ● ● ● ●

Acetaldehyde, (R)

▲ ▲ ▲ ▲

▲

▲ ▲ ▲ ▲

▲

▲

▲

PAN, (R)

ALD2, (R)

PAN, (R)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.5

1.0

1.5

2.0

H o u r s, L D T

VOC, ppmC

June 26, 

■

■

■

■

■

■ ■ ■ ■ ■ ■ ■

Isoprene, (L)

◆ ◆ ISOP, (L)

◆ ◆ ◆

◆ ◆

◆

◆

◆

◆

◆

◆

◆

◆

◆

◆

◆

◆ ◆ ◆

HCHO, (R)

▲ ▲ ▲ ▲ ▲

▲

▲ ▲

▲

▲

▲

PAN, (R)

FORM, (R)

CO, (R)

PAN, (R)
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

● ● ● ● ● ● ●

NO, (L) NO2

, (L)

PAN, (L)

NO, (L) NO2, (L)

PAN, (L)

TotNO3, (L)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

1.92 ppmC Isoprene June 26, 

O3, (L)

● ● ●

NO, (L) NO2

, (L)

CB05 Simulation O3, (L)

NO, (L)

NO2, (L)

PAN, (L)

TotNO3, (L)

Delta Isoprene
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

H o u r s, L D T

NO, 

O3, (L

●

PAN, (L)

O

N

N

P

T

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

H o u r s, L D T

NO, NO2, ppm

1.5 ppmC SynUrban + 0.15 ppmC Isoprene August 06, 

O3, (L)

● ●

NO, (L)

NO2, (L)

CB05 Simulation

O

N

N

P

T

Matched SynUrban and NOx with Isoprene added BLUE
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●●

●
 6 7 8 9 10 11 12 13 14 15 

 0

 1

 2

 3

 4

H o u r s, L D T

VO

▲

▲

▲

▲

▲

ISOP

ALD2 FORM

● ● ●

●

●

● ● ●

●

●

●

●

●

●

●

Acetic Acid ,ppm

 6 7 8 9 10 11 12 13 14 15 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

H o u r s, L D T

VOC, ppmC

September 11

▲ ▲

▲

▲

▲

▲ ▲ ▲

Isoprene

●

● ● ISOP

●

●

●

●

●

●

Formic Acid ,ppm

● ● ● ●

●

●

●

●

●

Acetic Acid ,ppm
 6 7 8 9 10 11 12 13 14 15 

 0

 1

 2

 3

 4

H o u r s, L D T

VO

▲

▲

▲

▲

▲

ISOP

FORM

● ● ●

●

● ● ●

●

●

●

● ● ● ●

●

●

●

● ● ●

Formic Acid ,ppm

 6 7 8 9 10 11 12 13 14 15 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

H o u r s, L D T

VOC, ppmC

September 11

▲ ▲

▲

▲

▲

▲ ▲ ▲

Isoprene

● ●

● ISOP

●

●

●

●

●

Methacrolein

● ●

●

●

●

●

●

●

Methylvinylketone

● ● ● ●

●

●

●

●

●

Formic Acid ,ppm
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

O3, (L)

● ● ● ●

NO, (L)

NO2, (L)

PAN, (L)

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

7.47 ppmC Isoprene September 11

O3, (L)

● ●

NO, (L)

NO2, (L)

7.47 ppmC Isoprene BLUE

O3, (L)

NO, (L) NO2, (L)

PAN, (L)

TotNO3, (L)

Matched Isoprene; Delta NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

H o u r s, L D T

CCl

4, relative

September 11

CCl4, (L) CCl4, (R)
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

H o u r s, L D T

VO

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

■

■

■ ■ ■ ■ ■

T

IS

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 1

 2

 3

 4

 5

 6

 7

 8

 9

 10

 11

 12

 13

 14

 15

H o u r s, L D T

VOC, ppmC

September 24

■ ■

■

■

■

■

■

■

■

■

Toluene, (L)

T

●

●▲

▲▲

▲▲▲▲▲▲▲▲▲▲▲

▲▲▲▲

▲▲

▲▲

CO, (R)

▲

▲ ▲

▲ ▲

▲ ▲

▲

▲

▲

▲

▲ ▲ ▲

HCHO, (R)

F
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

●

● ● ● ● ● ● ● ● ●

PAN, (L)

O

N

N

P

T

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

13.37 ppmC Toluene September 24

O3, (L)

● ● ● ● ●

NO, (L)

NO2, (L)

CB05 Simulation

O

N

N

P

T

Toluene vs Isoprene
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

● ● ●

●●●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

H o u r s, L D T

CCl

4, relative

September 24

● ● ● ● ● ● ● ● ● ● ●

CCl4, (L)

C

● ● ● ● ● ● ● ● ● ●

CCl4, (R)

C
Urban Mixture 

JN 19 97 

AU 26 01 

ST 10 99 

ST 12 94 

ST 14 00 

ST 14 94 

ST 15 94 

ST 26 99 

07/05 142
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

H o u r s, L D T

NO, 

●

PAN, 

NO

NO

PA

To

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

0.50

H o u r s, L D T

NO, NO2, ppm

1.96 ppmC SynUrban June 19, 

O3, (L)

● ●

NO, (L)

NO2, (L)

CB05 Simulation

O3

NO

NO

PA

To

Matched SynUrban and NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

H o u r s, L D T

NO, 

● ● ● ●●

● ●

PAN, 

O

N

N

P

T

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

H o u r s, L D T

NO, NO2, ppm

1.474 ppmC SynUrban Aug 26, 

● ● ● ● ● ●

O3, (L)

NO, (L)

NO2, (L)

CB05 Simulation

O

N

N

P

T

Matched SynUrban; Matched NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

 5

 6

 7

 8

 9

 10

 11

 12

H o u r s, L D T

CCl

4, relative

Aug 26, 

● ● ● ●

●

● ●

●

●

●

●

●

CCl4, (L)

C

●

●

●

●

●

●

●

●

●

●

●

CCl4, (R)

C
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.05

0.10

H o u r s, L D T

NO, 

● ●

PAN, (L)

NO, (

PAN, 

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.05

0.10

0.15

0.20

0.25

0.30

H o u r s, L D T

NO, NO2, ppm

1.474 ppmC SynUrban Sep 10, 

●

O3, (L)

NO, (L)

NO2, (L)

CB05 Simulation

O3, (

NO, (

NO2, 

PAN, 

TotN

Matched SynUrban and NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

●●

●●

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

CCl4, relative

Sep 10, 

CCl4CCl4
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

H o u r s, L D T

NO, 

●

PAN, (L)

N

N

P

T

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

H o u r s, L D T

NO, NO2, ppm

2.0 ppmC SynURB September 12

O3, (L

●

NO, (L)

NO2, (L)

CB05 Simulation

O

N

N

P

T

Matched SynURB
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.5

H o u r s, L D T

VO

▲ ▲ ▲ ▲ ▲

▲

▲ ▲

▲

▲

▲

▲ ▲

▲ ▲ ▲ ▲

▲ ▲ ▲

▲ ▲

HCHO, (R)

O

F

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.5

1.0

1.5

2.0

H o u r s, L D T

VOC, ppmC

September 12

P

▲ ▲ ▲ ▲ ▲

▲ ▲

▲

▲

▲

▲

▲ ▲

▲ ▲ ▲ ▲

▲ ▲ ▲

▲ ▲

HCHO, (R)

O

F
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

H o u r s, L D T

VO

■ ■ ■

■ ■

■ ■

■

■ ■

■

■

Acetaldehyde

■ ■ ■

■

■

■

■

ALD2

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲

Formaldehy

FOR

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

1.5

H o u r s, L D T

VOC, ppmC

Sep 14, 

▲ ▲

▲

▲

▲

▲ ▲ ▲ ▲

Formaldehyde, (R)

FOR
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

H o u r s, L D T

NO, 

● ● ●

NO, (L)

NO2, (L)

NO, (

NO2, 

TotN

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H o u r s, L D T

NO, NO2, ppm

6.0 ppmC SynUrban Sep 14, 

O3, (L)

NO, (L) NO2

, (L)

CB05 Simulation

O3, (

NO, (

NO2, 

TotN

Butyraldehyde vs SynUrban; matched NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

●
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.05

H o u r s, L D T

VO

▲ ▲ ▲ ▲

▲

▲

▲

▲

▲

▲

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.05

0.10

0.15

0.20

H o u r s, L D T

VOC, ppmC

September 14

▲

▲ ▲

▲

▲

▲

▲

▲ ▲

▲

▲

▲

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ 

HCHO, (R)
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

H o u r s, L D T

NO, 

● ●

●

PAN, 

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.10

0.20

0.30

0.40

H o u r s, L D T

NO, NO2, ppm

2.0 ppmC SynURB September 14

● ● ● ●

O3, (L)

● 

NO, (L)

NO2, (L)

CB05 Simulation

SynURB vs SynURB/SynE85
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

●

●

●

●

●●
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.05

H o u r s, L D T

VO

▲

▲ ▲ ▲ ▲

▲ ▲

▲

▲

▲

▲

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.05

0.10

0.15

0.20

H o u r s, L D T

VOC, ppmC

September 15

▲ ▲

▲ ▲

▲ ▲

▲

▲

▲

▲

▲

▲

▲

▲

▲ ▲

▲ ▲ ▲ ▲ ▲

HCHO, (R)

FOR
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.05

0.10

H o u r s, L D T

NO, 

PAN, 

O3, (

NO, (

PAN, 

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.05

0.10

0.15

0.20

0.25

0.30

H o u r s, L D T

NO, NO2, ppm

2.0 ppmC SynURB September 15

●

O3, 

●

NO, (L) NO2

, (L)

CB05 Simulation

O3, (

NO, (

NO2, 

PAN, 

TotN

SynURB vs SynURB/SynE85 (no EtOH)
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

●

●

●●
 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.05

0.10

H o u r s, L D T

NO, 

● ●

O3, (L)

PAN, (L)

O3

NO

PA

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.05

0.10

0.15

0.20

0.25

0.30

H o u r s, L D T

NO, NO2, ppm

1.474 ppmC SynUrban Sep 26, 

● ●

O3, (L)

NO, (L)

NO2, (L)

CB05 Simulation

O3

NO

NO

PA

To

4% SynUrban Difference; Matched NOx
 5 6 7 8 9 10 11 12 13 14 15 16 17 

 0

 10

 20

 30

 40

H o u r s, L D T

Temp., Dew Pt.°F; UV, m

 5 6 7 8 9 10 11 12 13 14 15 16 17 

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

H o u r s, L D T

CCl4, relative

Sep 26,